TWI888104B - Resist material, resist composition, patterning process, and monomer - Google Patents

Abstract

The present invention is a resist material containing a repeating unit-a containing a sulfonium salt or iodonium salt of a monovalent aromatic carboxylic acid that is iodinated, is substituted or unsubstituted, and is bonded to a polymer main chain via an ester bond. This provides: a resist material having higher sensitivity and higher resolution than conventional positive resist materials, small edge roughness and size variation, and excellent pattern profile after exposure; a resist composition containing the resist material; a patterning process; and a monomer to be an ingredient for the resist material.

Description

Resist material, resist composition, pattern forming method, and monomer

The present invention relates to a resist material, a resist composition, a pattern forming method, and a monomer.

With the high integration and high speed of LSI, the miniaturization of pattern rules is also progressing rapidly. The reason is that the popularization of 5G high-speed communication and artificial intelligence (AI) requires high-performance devices to handle them. As for the most advanced miniaturization technology, mass production of 5nm node devices using extreme ultraviolet (EUV) lithography with a wavelength of 13.5nm is already underway. In addition, discussions are underway on the use of EUV lithography for the next generation 3nm node and the next generation 2nm node devices.

As miniaturization progresses, image blurring caused by acid diffusion becomes a problem. In order to ensure the resolution of fine patterns below 45nm in size, some people have proposed that it is not only important to improve the dissolution contrast as previously advocated, but also to control acid diffusion (non-patent document 1). However, since chemically amplified resist materials use acid diffusion to improve sensitivity and contrast, if the post-exposure baking (PEB) temperature is lowered or the time is shortened to suppress acid diffusion to the limit, the sensitivity and contrast will also be significantly reduced.

The triangle trade-off relationship between sensitivity, resolution, and edge roughness is shown. In order to improve resolution, acid diffusion must be suppressed, but if the acid diffusion distance is shortened, the sensitivity will decrease.

It is effective to add an acid generator that generates a bulky acid to inhibit acid diffusion. Therefore, it has been proposed that the polymer contains repeating units from an onium salt having a polymerizable unsaturated bond. In this case, the polymer can also function as an acid generator (polymer-bonded acid generator). Patent document 1 has proposed coronium salts and iodonium salts having a polymerizable unsaturated bond that generate specific sulfonic acids. Patent document 2 has proposed coronium salts in which sulfonic acid is directly bonded to the main chain.

Some people have proposed using a cobalt salt of a weak acid having a polymerizable group with a pKa of -0.8 or more as an inhibitor material for a polymer-bonded quencher of a base polymer in order to inhibit acid diffusion (Patent Documents 3 to 5). Patent Document 3 lists carboxylic acids, sulfonamides, phenols, hexafluoroalcohol, etc. as weak acids. [Prior Technical Documents] [Patent Documents]

[Patent Document 1] Japanese Patent Publication No. 2006-045311 [Patent Document 2] Japanese Patent Publication No. 2006-178317 [Patent Document 3] International Publication No. 2019/167737 [Patent Document 4] International Publication No. 2022/264845 [Patent Document 5] Japanese Patent Publication No. 2022-115072 [Non-patent Document]

[Non-patent document 1] SPIE Vol.6520 65203L-1(2007)

[The problem that the invention wants to solve]

The present invention is made in view of the above circumstances, and its purpose is to provide a resist material with higher sensitivity and higher resolution than the known positive resist material, and with small edge roughness and dimensional variation, and a good pattern shape after exposure, as well as a resist composition containing the above resist material, a pattern forming method, and a monomer that is a raw material of the above resist material. [Means for solving the problem]

To solve the above problems, the present invention provides a resist material comprising repeating units a containing a substituted or unsubstituted iodinated monovalent aromatic carboxylic acid of a stibnium salt or an iodonium salt bonded to a polymer main chain via an ester bond.

Such a resist material can have a higher sensitivity and a higher resolution than conventional positive resist materials, and has small edge roughness and dimensional variation, and a good pattern shape after exposure.

In the present invention, the aforementioned repeating unit a preferably comprises a repeating unit represented by the following general formula (a)-1 or (a)-2. In the formula, ^RA is a hydrogen atom or a methyl group. ^X1' is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing an ester bond or an ether bond, and may also have one or more selected from a halogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a nitro group, and a cyano group. ^X2 is a single bond or a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and may also contain one or more selected from an ester group, an ether group, an amide group, a lactone ring, a sultone ring, and a halogen atom. ^X3 is a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms and not containing a fluorine atom, and may also have one or more selected from an ether group and an ester group. Y is a group selected from an ester group and a sulfonate group. ^R1 is independently a linear or branched alkyl group, alkoxy group, acyloxy group, or halogen atom other than iodine having 1 to 4 carbon atoms. m is an integer of 1 to 4, and n is an integer of 0 to 3. ^R2 to ^R6 are independently a monovalent alkyl group having 1 to 25 carbon atoms which may contain a heteroatom. In addition, any two of ^R2 , ^R3 , and ^R4 may be bonded to each other and form a ring together with the sulfur atom to which they are bonded.

The repeating unit a is preferably of such a structure.

In the above general formulae (a)-1 and (a)-2, ^X2 is preferably a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and may contain one or more selected from an ester group, an ether group, an amide group, a lactone ring, a sultone ring, and a halogen atom.

It is more preferable that the repeated unit a has such a structure.

In the present invention, it is preferred to further contain repeating units b in which the hydrogen atoms of either or both of the carboxyl group and the phenolic hydroxyl group are substituted with acid-labile groups.

Such a resist material can provide a resist material with higher sensitivity and less dimensional variation.

In this case, the aforementioned complex unit b is preferably at least one selected from the repeating units represented by the following general formulae (b1) and (b2). In the formula, ^RA is independently a hydrogen atom or a methyl group. ^Y1 is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and having an ester bond, an ether bond, or a lactone ring. ^Y2 is a single bond, an ester bond, or an amide bond. ^R11 and ^R12 are acid-unstable groups. ^R13 is a fluorine atom, a trifluoromethyl group, a cyano group, or an alkyl group having 1 to 6 carbon atoms. ^R14 is a single bond or a linear or branched alkanediyl group having 1 to 6 carbon atoms, and a portion of the carbon atoms thereof may be substituted by an ether bond or an ester bond. a is 1 or 2. b is an integer of 0 to 4.

The repeating unit b is preferably of such a structure.

Furthermore, in the present invention, the aforementioned resist material preferably further contains a repeating unit c having an adhesive group selected from a hydroxyl group, a carboxyl group, a lactone ring, a carbonate group, a thiocarbonate group, a carbonyl group, a cyclic acetal group, an ether bond, an ester bond, a sulfonate bond, a cyano group, an amide group, -O-C(=O)-S-, and -O-C(=O)-NH-.

Such a resist material can have excellent adhesion to the substrate.

In the present invention, the resist material preferably further contains at least one repeating unit d selected from the repeating units represented by the following general formulae (d1) to (d3). In the formula, ^RA is independently a hydrogen atom or a methyl group. ^Z1 is a single bond, a phenylene group, ^-OZ11- , -C(=O) ^-OZ11- or -C(=O)-NH- ^Z11- , ^Z11 is an alkanediyl group having 1 to 6 carbon atoms, an alkenediyl group having 2 to 6 carbon atoms or a phenylene group, and may contain at least one selected from a carbonyl group, an ester bond, an ether bond, and a hydroxyl group. ^{Z2A is a single bond or an ester bond. Z2B} is a single ^bond or a divalent group having 1 to 12 carbon atoms, and may contain at least one selected from an ester bond, an ether bond, a lactone ring, a bromine atom, and an iodine atom. Z ³ is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, -OZ ³¹ -, -C(=O)-OZ ³¹ - or -C(=O)-NH-Z ³¹ -, Z ³¹ is an alkanediyl group having 1 to 6 carbon atoms, an alkenediyl group having 2 to 6 carbon atoms or a phenylene group, and may contain at least one selected from a carbonyl group, an ester bond, an ether bond, a halogen atom, and a hydroxyl group. Rf ¹ to Rf ⁴ are independently a hydrogen atom, a fluorine atom or a trifluoromethyl group, but at least one of them is a fluorine atom. R ²¹ to R ²⁸ are independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. Furthermore, any two of R ²³ , R ²⁴ and R ²⁵ or any two of R ²⁶ , R ²⁷ and R ²⁸ may be bonded to each other and form a ring together with the sulfur atom to which they are bonded. ^{M -} is a non-nucleophilic relative ion.

Such a resist material can reduce acid diffusion and prevent a reduction in resolution due to blurring caused by acid diffusion.

In this case, the aforementioned Z ^2B preferably contains at least one iodine atom.

It is more preferable that the repeated unit d has such a structure.

In the present invention, the molecular weight of the above-mentioned resist material is preferably in the range of 1,000 to 100,000.

Such a resist material has excellent heat resistance, maintains alkaline solubility, and does not cause tailing after pattern formation.

Furthermore, the present invention provides a resist composition, which is characterized by containing the resist material described above.

Such a resist composition can have a higher sensitivity and a higher resolution than conventional positive resist materials, and has small edge roughness and dimensional variation, and a good pattern shape after exposure.

In this case, it is preferred to further contain at least one selected from the group consisting of an acid generator, an organic solvent, a quencher, and a surfactant.

Such substances may be added to the inhibitor composition of the present invention.

Furthermore, the present invention provides a pattern forming method, comprising the following steps: Using the resist composition described above to form a resist film on a substrate, Exposing the resist film to high-energy radiation, and Developing the exposed resist film using a developer.

Such a pattern forming method can form a pattern with a good pattern shape.

At this time, it is preferable to use i-rays, KrF excimer laser light, ArF excimer laser light, electron beams, or extreme ultraviolet light with a wavelength of 3 to 15 nm as the aforementioned high-energy radiation.

The pattern forming method of the present invention can use such high energy rays.

In addition, the present invention provides a monomer represented by the following general formula (a)-1M or (a)-2M. In the formula, ^RA is a hydrogen atom or a methyl group. ^X1 is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing an ester bond or an ether bond, and may also have a halogen atom. ^X2 is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and may also contain one or more selected from an ester group, an ether group, an amide group, a lactone ring, a sultone ring, and a halogen atom. ^X3 is a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms and not containing a fluorine atom, and may also have one or more selected from an ether group and an ester group. ^R1 is independently a linear or branched alkylene group having 1 to 4 carbon atoms, an alkoxy group, an acyloxy group, or a halogen atom other than iodine. m is an integer of 1 to 4, and n is an integer of 0 to 3. R ² to R ⁶ are each independently a monovalent hydrocarbon group having 1 to 25 carbon atoms which may contain a heteroatom. In addition, any two of R ² , R ³ and R ⁴ may be bonded to each other and form a ring together with the sulfur atom to which they are bonded.

In addition, the present invention provides a monomer represented by the following general formula (a)-1'M or (a)-2'M. [Chemistry 5] In the formula, ^RA is a hydrogen atom or a methyl group. ^X1' is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing an ester bond or an ether bond, and may also have one or more selected from a halogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a nitro group, and a cyano group. ^X2 is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and may also contain one or more selected from an ester group, an ether group, an amide group, a lactone ring, a sultone ring, and a halogen atom. ^X3 is a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms and not containing a fluorine atom, and may also have one or more selected from an ether group and an ester group. Y is a group selected from an ester group and a sulfonate group. ^R1 is independently a linear or branched alkyl group, alkoxy group, acyloxy group, or halogen atom other than iodine having 1 to 4 carbon atoms. m is an integer of 1 to 4, and n is an integer of 0 to 3. ^R2 to ^R6 are independently a monovalent alkyl group having 1 to 25 carbon atoms which may contain a heteroatom. In addition, any two of ^R2 , ^R3 , and ^R4 may be bonded to each other and form a ring together with the sulfur atom to which they are bonded.

If such a monomer is used, it can be used as a raw material of a resist material having higher sensitivity and higher resolution than conventional positive resist materials, and having small edge roughness and dimensional variation, and having a good pattern shape after exposure. [Effect of the invention]

The resist material of the present invention can improve the decomposition efficiency of the acid generator, so it has a high effect of inhibiting the diffusion of the acid, and is highly sensitive and has a high resolution. The pattern shape, edge roughness and size variation after exposure are small and good. Therefore, due to these excellent properties, it is extremely practical, especially as a fine pattern forming material for ultra-large integrated circuit manufacturing or EB drawing masks, and a pattern forming material for EB or EUV exposure. The positive resist material of the present invention can be applied not only to lithography during semiconductor circuit formation, but also to the formation of mask circuit patterns, micro-machines, and thin-film magnetic head circuit formation.

As described above, it is required to develop a resist material having higher sensitivity and higher resolution than the known positive resist material, with small edge roughness and dimensional variation, and a good pattern shape after exposure, as well as a resist composition containing the aforementioned resist material, a pattern forming method, and a monomer which is a raw material of the aforementioned resist material.

The inventors of this case have repeatedly conducted in-depth research to obtain positive type resist materials with high resolution, low edge roughness (LWR) and low dimensional variation (CDU) as required in recent years, and have obtained the following insights: it is necessary to shorten the acid diffusion distance to the limit, and the acid diffusion distance must be uniform at the molecular level, by using a polymer containing specific repeating units as the base polymer, and the repeating unit has a self-polymer The acid diffusion of the coronium salt or iodonium salt of a substituted or unsubstituted iodinated monovalent aromatic carboxylic acid bonded via an ester bond in the main chain becomes very small. In addition, the alkaline solubility of the iodinated monovalent aromatic carboxylic acid generated by exposure is low swelling. The two effects of making the acid diffusion distance uniform and the low swelling effect are effective in making the base polymer of a good chemical amplification resist material for LWR and CDU.

In addition, the following insights were obtained, which led to the completion of the present invention: in order to improve the solubility contrast, repeated units in which the hydrogen atoms of the carboxyl or phenolic hydroxyl groups are replaced by acid-unstable groups are introduced, thereby obtaining a material with high sensitivity and a greatly improved contrast of the alkali dissolution rates before and after exposure, and a high sensitivity and a high effect of inhibiting acid diffusion, high resolution, and small and good variations in the shape, edge roughness, and size of the pattern after exposure, and is particularly suitable as a resist material for use in the manufacture of very large integrated circuits or as a material for forming fine patterns of masks.

That is, the present invention is a resist material comprising a repeating unit a containing a substituted or unsubstituted iodinated monovalent aromatic carboxylic acid of a stibnium salt or an iodonium salt bonded to a polymer main chain via an ester bond.

Furthermore, the present invention is a monomer represented by the following general formula (a)-1M or (a)-2M. In the formula, ^RA is a hydrogen atom or a methyl group. ^X1 is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing an ester bond or an ether bond, and may also have a halogen atom. ^X2 is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and may also contain one or more selected from an ester group, an ether group, an amide group, a lactone ring, a sultone ring, and a halogen atom. ^X3 is a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms and not containing a fluorine atom, and may also have one or more selected from an ether group and an ester group. ^R1 is independently a linear or branched alkylene group having 1 to 4 carbon atoms, an alkoxy group, an acyloxy group, or a halogen atom other than iodine. m is an integer of 1 to 4, and n is an integer of 0 to 3. R ² to R ⁶ are each independently a monovalent hydrocarbon group having 1 to 25 carbon atoms which may contain a heteroatom. In addition, any two of R ² , R ³ and R ⁴ may be bonded to each other and form a ring together with the sulfur atom to which they are bonded.

Furthermore, the present invention is a monomer represented by the following general formula (a)-1'M or (a)-2'M. [Chemistry 7] In the formula, ^RA is a hydrogen atom or a methyl group. ^X1' is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing an ester bond or an ether bond, and may also have one or more selected from a halogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a nitro group, and a cyano group. ^X2 is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and may also contain one or more selected from an ester group, an ether group, an amide group, a lactone ring, a sultone ring, and a halogen atom. ^X3 is a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms and not containing a fluorine atom, and may also have one or more selected from an ether group and an ester group. Y is a group selected from an ester group and a sulfonate group. ^R1 is independently a linear or branched alkyl group, alkoxy group, acyloxy group, or halogen atom other than iodine having 1 to 4 carbon atoms. m is an integer of 1 to 4, and n is an integer of 0 to 3. ^R2 to ^R6 are independently a monovalent alkyl group having 1 to 25 carbon atoms which may contain a heteroatom. In addition, any two of ^R2 , ^R3 , and ^R4 may be bonded to each other and form a ring together with the sulfur atom to which they are bonded.

The present invention is described in detail below, but the present invention is not limited thereto.

[Monomer] The present invention is a monomer represented by the following general formula (a)-1M or (a)-2M. [Chemistry 8] In the formula, ^RA is a hydrogen atom or a methyl group. ^X1 is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing an ester bond or an ether bond, and may also have a halogen atom. ^X2 is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and may also contain one or more selected from an ester group, an ether group, an amide group, a lactone ring, a sultone ring, and a halogen atom. ^X3 is a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms and not containing a fluorine atom, and may also have one or more selected from an ether group and an ester group. ^R1 is independently a linear or branched alkylene group having 1 to 4 carbon atoms, an alkoxy group, an acyloxy group, or a halogen atom other than iodine. m is an integer of 1 to 4, and n is an integer of 0 to 3. R ² to R ⁶ are each independently a monovalent hydrocarbon group having 1 to 25 carbon atoms which may contain a heteroatom. In addition, any two of R ² , R ³ and R ⁴ may be bonded to each other and form a ring together with the sulfur atom to which they are bonded.

In the formula, ^RA is a hydrogen atom or a methyl group, preferably a methyl group. ^X1 is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing an ester bond or an ether bond, and may also have a halogen atom, and is preferably a single bond or a group containing a phenylene group. ^X2 is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and may also contain one or more selected from an ester group, an ether group, an amide group, a lactone ring, a sultone ring, and a halogen atom, and is preferably a group containing an ether group. ^X3 is a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms and not containing a fluorine atom, and may also have one or more selected from an ether group and an ester group, and is preferably a single bond, a methylene group, an ethylene group, or a propylene group. ^R1 is independently a linear or branched alkyl group, alkoxy group, acyloxy group, or a halogen atom other than iodine with a carbon number of 1 to 4, preferably a fluorine atom. m is an integer of 1 to 4, and n is an integer of 0 to 3, preferably m=1 to 2, n=0 to 1. ^R2 to ^R6 are independently a monovalent hydrocarbon group with a carbon number of 1 to 25 which may contain a heteroatom, preferably an aromatic hydrocarbon group, more preferably a phenyl group, a naphthyl group, a biphenyl group, a phenyl sulfide group, a phenyl ether group, or a benzophenone group.

Furthermore, the present invention is a monomer represented by the following general formula (a)-1'M or (a)-2'M. [Chemistry 9] In the formula, ^RA is a hydrogen atom or a methyl group. ^X1' is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing an ester bond or an ether bond, and may also have one or more selected from a halogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a nitro group, and a cyano group. ^X2 is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and may also contain one or more selected from an ester group, an ether group, an amide group, a lactone ring, a sultone ring, and a halogen atom. ^X3 is a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms and not containing a fluorine atom, and may also have one or more selected from an ether group and an ester group. Y is a group selected from an ester group and a sulfonate group. ^R1 is independently a linear or branched alkyl group, alkoxy group, acyloxy group, or halogen atom other than iodine having 1 to 4 carbon atoms. m is an integer of 1 to 4, and n is an integer of 0 to 3. ^R2 to ^R6 are independently a monovalent alkyl group having 1 to 25 carbon atoms which may contain a heteroatom. In addition, any two of ^R2 , ^R3 , and ^R4 may be bonded to each other and form a ring together with the sulfur atom to which they are bonded.

In the formula, ^RA is a hydrogen atom or a methyl group, preferably a methyl group. ^X1' is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing an ester bond or an ether bond, and may have at least one selected from a halogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a nitro group, and a cyano group, and may be a single bond or a group containing a phenylene group. ^X2 is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and may have at least one selected from an ester group, an ether group, an amide group, a lactone ring, a sultone ring, and a halogen atom, and may contain at least one selected from a ether group. ^X3 is a straight or branched alkylene group with 1 to 6 carbon atoms, which is a single bond or does not contain fluorine atoms, and may have at least one selected from ether groups and ester groups, and is preferably a single bond, a methylene group, an ethylene group or a propylene group. Y is a group selected from ester groups and sulfonate groups. ^R1 is independently a straight or branched alkylene group with 1 to 4 carbon atoms, an alkoxy group, an acyloxy group, or a halogen atom other than iodine, and is preferably a fluorine atom. m is an integer of 1 to 4, and n is an integer of 0 to 3, and preferably m=1 to 2 and n=0 to 1. ^R2 to ^R6 are independently a monovalent hydrocarbon group with 1 to 25 carbon atoms, which may also contain heteroatoms, and are preferably aromatic hydrocarbon groups, and are more preferably phenyl, naphthyl, biphenyl, phenyl sulfide, phenyl ether, or benzophenone groups.

[Resistance material] The resistance material of the present invention contains a repeating unit a containing a substituted or unsubstituted iodinated monovalent aromatic carboxylic acid of a coronium salt or an iodonium salt bonded to the polymer main chain via an ester bond. The monovalent aromatic carboxylic acid is preferably benzoic acid. The repeating unit a preferably includes a repeating unit represented by the following general formula (a)-1 or (a)-2. [Chemical 10] In the formula, ^RA is a hydrogen atom or a methyl group. ^X1' is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing an ester bond or an ether bond, and may also have one or more selected from a halogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a nitro group, and a cyano group. ^X2 is a single bond or a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and may also contain one or more selected from an ester group, an ether group, an amide group, a lactone ring, a sultone ring, and a halogen atom. ^X3 is a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms and not containing a fluorine atom, and may also have one or more selected from an ether group and an ester group. Y is a group selected from an ester group and a sulfonate group. ^R1 is independently a linear or branched alkyl group, alkoxy group, acyloxy group, or halogen atom other than iodine having 1 to 4 carbon atoms. m is an integer of 1 to 4, and n is an integer of 0 to 3. ^R2 to ^R6 are independently a monovalent alkyl group having 1 to 25 carbon atoms which may contain a heteroatom. In addition, any two of ^R2 , ^R3 , and ^R4 may be bonded to each other and form a ring together with the sulfur atom to which they are bonded.

In the above general formulas (a)-1 and (a)-2, the above ^X2 is preferably a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and may contain one or more selected from an ester group, an ether group, an amide group, a lactone ring, a sultone ring, and a halogen atom. When ^X2 has a structure other than a single bond, the flexibility of the stibnium salt and the iodonium salt is increased, thereby improving the ability to quench the acid.

Copper or iodine decomposes by photolysis and becomes an iodinated monovalent aromatic carboxylic acid bonded to the polymer. The iodinated monovalent aromatic carboxylic acid has the characteristic of low swelling in alkaline developer. The low swelling property can reduce the decrease in dimensional uniformity caused by swelling during the development of contact hole patterns, or reduce the stress on the pattern during the rotation drying of the line and space pattern after rinsing with pure water, and reduce the pattern collapse after the pattern is formed.

The aforementioned repeating unit a is a quencher having a structure of a substituted or unsubstituted iodinated monovalent aromatic carboxylic acid of a coronium salt or an iodonium salt, and is a quencher-bonded polymer. The quencher-bonded polymer has a high effect of inhibiting acid diffusion and has the characteristics of excellent resolution as mentioned above. Thus, high resolution, low LWR and low CDU can be achieved.

The monomers providing the repeating unit a1 represented by the general formula (a)-1 and the repeating unit a2 represented by the general formula (a)-2 can be the monomers of the present invention described above. The anion part can be the following, but is not limited thereto. In the following formula, ^RA is the same as above.

[Chemistry 11]

[Chemistry 12]

[Chemistry 13]

[Chemistry 14]

[Chemistry 15]

[Chemistry 16]

[Chemistry 17]

[Chemistry 18]

[Chemistry 19]

[Chemistry 20]

[Chemistry 21]

[Chemistry 22]

[Chemistry 23]

[Chemistry 24]

[Chemistry 25]

[Chemistry 26]

The cations of the cobalt salt represented by the general formula (a)-1 are listed below, but are not limited thereto. [Chemistry 27]

[Chemistry 28]

[Chemistry 29]

[Chemistry 30]

[Chemistry 31]

[Chemistry 32]

[Chemistry 33]

[Chemistry 34]

[Chemistry 35]

[Chemistry 36]

[Chemistry 37]

[Chemistry 38]

[Chemistry 39]

[Chemistry 40]

[Chemistry 41]

[Chemistry 42]

[Chemistry 43]

[Chemistry 44]

[Chemistry 45]

[Chemistry 46]

[Chemistry 47]

[Chemistry 48]

[Chemistry 49]

The cations of the iodonium salt represented by the general formula (a)-2 are listed below, but are not limited thereto.

[Chemistry 50]

In order to improve the solubility contrast, the above-mentioned resist material preferably further contains a repeating unit b in which the hydrogen atoms of either or both of the carboxyl group and the phenolic hydroxyl group are replaced by acid-unstable groups. In addition, the above-mentioned repeating unit b is preferably at least one selected from the repeating units represented by the following general formulas (b1) and (b2). Hereinafter, the repeating unit in which the hydrogen atoms of the carboxyl group are replaced by acid-unstable groups is referred to as a repeating unit b1, and the repeating unit in which the hydrogen atoms of the phenolic hydroxyl group are replaced by acid-unstable groups is referred to as a repeating unit b2.

The repeating units b1 and b2 can be represented by the following general formulas (b1) and (b2), respectively. In the formula, ^RA is independently a hydrogen atom or a methyl group. ^Y1 is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and having an ester bond, an ether bond, or a lactone ring. ^Y2 is a single bond, an ester bond, or an amide bond. ^R11 and ^R12 are acid-unstable groups. ^R13 is a fluorine atom, a trifluoromethyl group, a cyano group, or an alkyl group having 1 to 6 carbon atoms. ^R14 is a single bond or a linear or branched alkanediyl group having 1 to 6 carbon atoms, and a portion of the carbon atoms thereof may be substituted by an ether bond or an ester bond. a is 1 or 2. b is an integer of 0 to 4.

In the formula, ^RA is independently a hydrogen atom or a methyl group, preferably a methyl group. ^Y1 is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and having an ester bond, an ether bond, or a lactone ring, preferably a single bond or a phenylene group. ^Y2 is a single bond, an ester bond, or an amide bond, preferably a single bond. ^R11 and ^R12 are acid-unstable groups. ^R13 is a fluorine atom, a trifluoromethyl group, a cyano group, or an alkyl group having 1 to 6 carbon atoms, preferably a fluorine atom. ^R14 is a single bond or a linear or branched alkanediyl group having 1 to 6 carbon atoms, and a part of the carbon atoms thereof may be substituted by an ether bond or an ester bond, preferably an ester bond. a is 1 or 2, preferably 1. b is an integer of 0 to 4, preferably 0 or 1.

The monomers providing the repeating unit b1 may be listed as follows, but are not limited thereto. In the following formula, ^RA and R ¹¹ are the same as those described above. [Chemical 52]

[Chemistry 53]

The monomers providing the repeating unit b2 may be exemplified as follows, but are not limited thereto. In the following formula, ^RA and ^R12 are the same as those described above. [Chem. 54]

There are various options for the acid-labile group represented by R ¹¹ or R ¹² , for example, those represented by the following general formulas (AL-1) to (AL-3). [Chemistry 55]

In the general formula (AL-1), c is an integer of 0 to 6. ^RL1 is a tertiary alkyl group having 4 to 61 carbon atoms, preferably 4 to 15 carbon atoms, a trialkylsilyl group in which each alkyl group is a saturated alkyl group having 1 to 6 carbon atoms, a saturated alkyl group having 4 to 20 carbon atoms and containing a carbonyl group, an ether bond or an ester bond, or a group represented by the general formula (AL-3).

The tertiary alkyl represented by R ^L1 may be saturated or unsaturated, and may be branched or cyclic. Specific examples thereof include tertiary butyl, tertiary pentyl, 1,1-diethylpropyl, 1-ethylcyclopentyl, 1-butylcyclopentyl, 1-ethylcyclohexyl, 1-butylcyclohexyl, 1-ethyl-2-cyclopentenyl, 1-ethyl-2-cyclohexenyl, 2-methyl-2-adamantyl, etc. The aforementioned trialkylsilyl may include trimethylsilyl, triethylsilyl, dimethyltertiary butylsilyl, etc. The aforementioned saturated alkyl group containing a carbonyl group, an ether bond or an ester bond may be in any of the linear, branched or cyclic forms, and is preferably in the form of a ring. Specific examples thereof include 3-oxocyclohexyl, 4-methyl-2-oxocyclohexane-4-yl, 5-methyl-2-oxocyclopentane-5-yl, 2-tetrahydropyranyl, 2-tetrahydrofuranyl and the like.

Examples of the acid-labile group represented by the general formula (AL-1) include tertiary butoxycarbonyl, tertiary butoxycarbonylmethyl, tertiary pentyloxycarbonyl, tertiary pentyloxycarbonylmethyl, 1,1-diethylpropyloxycarbonyl, 1,1-diethylpropyloxycarbonylmethyl, 1-ethylcyclopentyloxycarbonyl, 1-ethylcyclopentyloxycarbonylmethyl, 1-ethyl-2-cyclopentenyloxycarbonyl, 1-ethyl-2-cyclopentenyloxycarbonylmethyl, 1-ethoxyethoxycarbonylmethyl, 2-tetrahydropyranyloxycarbonylmethyl, and 2-tetrahydrofuranyloxycarbonylmethyl.

In addition, the acid-labile group represented by the general formula (AL-1) can also be exemplified by the following general formulas (AL-1)-1 to (AL-1)-10. In the formula, the dotted lines are atomic bonds.

In the general formulae (AL-1)-1 to (AL-1)-10, c is the same as described above. ^{R L8} is independently a saturated alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. R ^L9 is a hydrogen atom or a saturated alkyl group having 1 to 10 carbon atoms. R ^L10 is a saturated alkyl group having 2 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. The saturated alkyl group may be in a linear, branched or cyclic form.

In the general formula (AL-2), R ^L2 and R ^L3 are independently a hydrogen atom or a saturated alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. The saturated alkyl group may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, dibutyl, tertiary butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, n-octyl and the like.

In the general formula (AL-2), R ^L4 is a alkyl group having 1 to 18 carbon atoms and preferably 1 to 10 carbon atoms, which may contain impurity atoms. The aforementioned alkyl group may be saturated or unsaturated, and may be in any of the forms of a straight chain, a branched chain, or a ring. The aforementioned alkyl group may include saturated alkyl groups having 1 to 18 carbon atoms, and a portion of the hydrogen atoms thereof may be substituted by a hydroxyl group, an alkoxy group, a pendoxy group, an amino group, an alkylamino group, or the like. Such substituted saturated alkyl groups may include the following. [Chemistry 57] In the formula, the dotted lines are atomic bonds.

^RL2 and ^RL3 , ^RL2 and ^RL4 , or ^RL3 and ^RL4 may also bond to each other and form a ring together with the carbon atom to which they are bonded or together with the carbon atom and the oxygen atom. In this case, ^RL2 and ^RL3 , ^RL2 and ^RL4 , or ^RL3 and ^RL4 participating in the formation of the ring are each independently an alkanediyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. The carbon number of the ring obtained by the bonding is preferably 3 to 10, more preferably 4 to 10.

Among the acid-labile groups represented by the general formula (AL-2), the linear or branched ones can be exemplified by the following formulas (AL-2)-1 to (AL-2)-69, but are not limited thereto. In the following formula, the dashed line represents an atomic bond. [Chemistry 58]

[Chemistry 59]

[Chemistry 60]

[Chemistry 61]

Among the acid-labile groups represented by the general formula (AL-2), examples of cyclic groups include tetrahydrofuran-2-yl, 2-methyltetrahydrofuran-2-yl, tetrahydropyran-2-yl, and 2-methyltetrahydropyran-2-yl.

In addition, the acid-unstable group may be a group represented by the following general formula (AL-2a) or (AL-2b). The inhibitor material may also be cross-linked between molecules or within molecules by the acid-unstable group. [Chemistry 62] In the formula, the dotted lines are atomic bonds.

In the general formula (AL-2a) or (AL-2b), R ^L11 and R ^L12 are each independently a hydrogen atom or a saturated alkyl group having 1 to 8 carbon atoms. The saturated alkyl group may be in a linear, branched, or cyclic form. Furthermore, R ^L11 and R ^L12 may be bonded to each other and form a ring together with the carbon atoms to which they are bonded. In this case, R ^L11 and R ^L12 are each independently an alkanediyl group having 1 to 8 carbon atoms. ^{R L13} is each independently a saturated alkylene group having 1 to 10 carbon atoms. The saturated alkylene group may be in a linear, branched, or cyclic form. d and e are independently integers between 0 and 10, preferably between 0 and 5, and f is an integer between 1 and 7, preferably between 1 and 3.

In the general formula (AL-2a) or (AL-2b), ^LA is a (f+1)-valent aliphatic saturated alkyl group having 1 to 50 carbon atoms, a (f+1)-valent alicyclic saturated alkyl group having 3 to 50 carbon atoms, a (f+1)-valent aromatic alkyl group having 6 to 50 carbon atoms, or a (f+1)-valent heterocyclic group having 3 to 50 carbon atoms. In addition, part of the carbon atoms of these groups may be substituted by a group containing a heteroatom, and part of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted by a hydroxyl group, a carboxyl group, an acyl group or a fluorine atom. ^LA is preferably a saturated alkylene group having 1 to 20 carbon atoms, a saturated alkylene group such as a trivalent saturated alkyl group or a tetravalent saturated alkyl group, or an arylene group having 6 to 30 carbon atoms. The saturated alkyl group may be in the form of a straight chain, a branched chain, or a ring. ^LB is -C(=O)-O-, -NH-C(=O)-O-, or -NH-C(=O)-NH-.

Examples of the cross-linked acetal group represented by the general formula (AL-2a) or (AL-2b) include the following groups represented by the formulas (AL-2)-70 to (AL-2)-77. In the formula, the dotted lines are atomic bonds.

In the general formula (AL-3), R ^L5 , R ^L6 and R ^L7 are independently alkyl groups having 1 to 20 carbon atoms, and may contain heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and fluorine atoms. The aforementioned alkyl groups may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include: alkyl groups having 1 to 20 carbon atoms, cyclic saturated alkyl groups having 3 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cyclic unsaturated alkyl groups having 3 to 20 carbon atoms, and aryl groups having 6 to 10 carbon atoms. Furthermore, R ^L5 and R ^L6 , R ^L5 and R ^L7 , or R ^L6 and R ^L7 may be bonded to each other and form an alicyclic ring having 3 to 20 carbon atoms together with the carbon atoms to which they are bonded.

The groups represented by the general formula (AL-3) include tertiary butyl, 1,1-diethylpropyl, 1-ethylnorbornyl, 1-methylcyclopentyl, 1-isopropylcyclopentyl, 1-ethylcyclopentyl, 1-methylcyclohexyl, 2-(2-methyl)adamantyl, 2-(2-ethyl)adamantyl, tertiary pentyl, and the like.

In addition, the group represented by the general formula (AL-3) can also be exemplified by the groups represented by the following general formulas (AL-3)-1 to (AL-3)-19. In the formula, the dotted lines are atomic bonds.

In the general formulae (AL-3)-1 to (AL-3)-19, ^RL14 is independently a saturated alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms. ^RL15 and ^RL17 are independently a hydrogen atom or a saturated alkyl group having 1 to 20 carbon atoms. ^RL16 is an aryl group having 6 to 20 carbon atoms. The saturated alkyl group may be linear, branched or cyclic. The aryl group is preferably a phenyl group or the like. ^RF is a fluorine atom or a trifluoromethyl group. g is an integer of 1 to 5.

In addition, the acid-unstable group may be a group represented by the following general formula (AL-3)-20 or (AL-3)-21. The inhibitor material may also be cross-linked intramolecularly or intermolecularly by the acid-unstable group. [Chemistry 65] In the formula, the dotted lines are atomic bonds.

In the general formula (AL-3)-20 and (AL-3)-21, R ^L14 is the same as the above. R ^L18 is a (h+1)-valent saturated alkylene group having 1 to 20 carbon atoms or a (h+1)-valent arylene group having 6 to 20 carbon atoms, and may contain heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms. The above-mentioned saturated alkylene group may be linear, branched, or cyclic. h is an integer of 1 to 3.

Examples of monomers that provide repeating units containing an acid-labile group represented by the general formula (AL-3) include (meth)acrylates having stereoisomer structures represented by the following general formula (AL-3)-22.

In the general formula (AL-3)-22, ^RA is the same as described above. ^RLc1 is a saturated alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted. The saturated alkyl group may be in a linear, branched, or cyclic form. ^RLc2 to ^RLc11 are each independently a hydrogen atom or a alkyl group having 1 to 15 carbon atoms which may contain a heteroatom. Examples of the heteroatom include an oxygen atom, etc. Examples of the alkyl group include an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 15 carbon atoms, etc. R ^Lc2 and R ^Lc3 , R ^Lc4 and R ^Lc6 , R ^Lc4 and R ^Lc7 , R ^Lc5 and R ^Lc7 , R ^Lc5 and R ^Lc11 , R ^Lc6 and R ^Lc10 , R ^Lc8 and R ^Lc9 , or R ^Lc9 and R ^Lc10 may also be bonded to each other and form a ring together with the carbon atoms to which they are bonded. In this case, the group involved in the bond is a alkylene group having 1 to 15 carbon atoms and may contain a heteroatom. In addition, R ^Lc2 and R ^Lc11 , R ^Lc8 and R ^Lc11 , or R ^Lc4 and R ^Lc6 may be bonded to adjacent carbon atoms without any group interposed therebetween to form a double bond. In addition, a mirror image is also represented by this formula.

Here, monomers providing repeating units represented by the general formula (AL-3)-22 include those described in Japanese Patent Publication No. 2000-327633. Specifically, the following monomers may be listed, but are not limited thereto. In the following formula, ^RA is the same as the above. [Chemistry 67]

Examples of monomers that provide repeating units containing an acid-labile group represented by the general formula (AL-3) include (meth)acrylates containing a furandiyl group, a tetrahydrofurandiyl group or an oxa-norbornanediyl group represented by the following general formula (AL-3)-23. [Chemistry 68]

In the general formula (AL-3)-23, ^RA is the same as described above. ^{R Lc12} and R ^Lc13 are independently alkyl groups having 1 to 10 carbon atoms. ^{R Lc12} and R ^Lc13 may also be bonded to each other and form an aliphatic ring together with the carbon atoms to which they are bonded. R ^Lc14 is furandiyl, tetrahydrofurandiyl or oxa-norbornanediyl. R ^Lc15 is a hydrogen atom or a alkyl group having 1 to 10 carbon atoms which may contain a heteroatom. The aforementioned alkyl group may be any of a linear chain, a branched structure, and a ring structure. Specific examples thereof include saturated alkyl groups having 1 to 10 carbon atoms.

The monomers providing the repeating unit represented by the general formula (AL-3)-23 are listed below, but are not limited thereto. In the following formula, ^RA is the same as above, Ac is an acetyl group, and Me is a methyl group. [Chemistry 69]

[Chemistry 70]

The aforementioned resist material may further contain repeating units c having an adhesion group selected from a hydroxyl group, a carboxyl group, a lactone ring, a carbonate group, a thiocarbonate group, a carbonyl group, a cyclic acetal group, an ether bond, an ester bond, a sulfonate bond, a cyano group, an amide group, -O-C(=O)-S-, and -O-C(=O)-NH-.

The monomers providing the repeating unit c can be listed as follows, but are not limited thereto. In the following formula, ^RA is the same as above. [Chemical 71]

[Chemistry 72]

[Chemistry 73]

[Chemistry 74]

[Chemistry 75]

[Chemistry 76]

[Chemistry 77]

[Chemistry 78]

The aforementioned resist material may also contain a repeating unit d from an onium salt containing a polymerizable unsaturated bond. The ideal repeating unit d can be listed as follows: a repeating unit represented by the following general formula (d1) (hereinafter also referred to as repeating unit d1), a repeating unit represented by the following general formula (d2) (hereinafter also referred to as repeating unit d2), and a repeating unit represented by the following general formula (d3) (hereinafter also referred to as repeating unit d3). In addition, the repeating units d1~d3 may be used alone or in combination of two or more. That is, the aforementioned resist material preferably contains at least one repeating unit d selected from the repeating units represented by the following general formulas (d1)~(d3). [Chemistry 79] In the formula, ^RA is independently a hydrogen atom or a methyl group. ^Z1 is a single bond, a phenylene group, ^-OZ11- , -C(=O) ^-OZ11- or -C(=O)-NH- ^Z11- , ^Z11 is an alkanediyl group having 1 to 6 carbon atoms, an alkenediyl group having 2 to 6 carbon atoms or a phenylene group, and may contain at least one selected from a carbonyl group, an ester bond, an ether bond, and a hydroxyl group. ^{Z2A is a single bond or an ester bond. Z2B} is a single ^bond or a divalent group having 1 to 12 carbon atoms, and may contain at least one selected from an ester bond, an ether bond, a lactone ring, a bromine atom, and an iodine atom. Z ³ is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, -OZ ³¹ -, -C(=O)-OZ ³¹ - or -C(=O)-NH-Z ³¹ -, Z ³¹ is an alkanediyl group having 1 to 6 carbon atoms, an alkenediyl group having 2 to 6 carbon atoms or a phenylene group, and may contain at least one selected from a carbonyl group, an ester bond, an ether bond, a halogen atom, and a hydroxyl group. Rf ¹ to Rf ⁴ are independently a hydrogen atom, a fluorine atom or a trifluoromethyl group, but at least one of them is a fluorine atom. R ²¹ to R ²⁸ are independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom. Furthermore, any two of R ²³ , R ²⁴ and R ²⁵ or any two of R ²⁶ , R ²⁷ and R ²⁸ may be bonded to each other and form a ring together with the sulfur atom to which they are bonded. ^{M -} is a non-nucleophilic relative ion.

In the formula, ^RA is independently a hydrogen atom or a methyl group, preferably a methyl group. ^Z1 is a single bond, a phenylene group, ^-OZ11- , -C(=O) ^-OZ11- or -C(=O)-NH- ^Z11- , ^Z11 is an alkanediyl group having 1 to 6 carbon atoms, an alkenediyl group having 2 to 6 carbon atoms or a phenylene group, and may contain at least one selected from a carbonyl group, an ester bond, an ether bond, and a hydroxyl group, and is preferably ether. ^Z2A is a single bond or an ester bond, preferably an ester bond. ^Z2B is a single bond or a divalent group having 1 to 12 carbon atoms, and may contain at least one selected from an ester bond, an ether bond, a lactone ring, a bromine atom, and an iodine atom. Z ³ is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, -OZ ³¹ -, -C(=O)-OZ ³¹ - or -C(=O)-NH-Z ³¹ -, Z ³¹ is an alkanediyl group having 1 to 6 carbon atoms, an alkenediyl group having 2 to 6 carbon atoms or phenylene, and may contain at least one selected from a carbonyl group, an ester bond, an ether bond, a halogen atom, and a hydroxyl group. Rf ¹ to Rf ⁴ are independently a hydrogen atom, a fluorine atom or a trifluoromethyl group, but at least one of them is a fluorine atom.

In the general formula (d2), ^Rf1 to ^Rf4 are independently hydrogen atoms, fluorine atoms or trifluoromethyl groups, but at least one of them is a fluorine atom. In particular, at least one of ^Rf3 and ^Rf4 is preferably a fluorine atom, and it is more preferred that both ^Rf3 and ^Rf4 are fluorine atoms.

In general formulae (d1) to (d3), R ²¹ to R ²⁸ are independently monovalent hydrocarbon groups having 1 to 20 carbon atoms which may contain impurities. In addition, any two of R ²³ , R ²⁴ and R ²⁵ or any two of R ²⁶ , R ²⁷ and R ²⁸ may be bonded to each other and form a ring together with the sulfur atom to which they are bonded. The monovalent hydrocarbon group may be linear, branched or cyclic, and specific examples thereof include alkyl groups having 1 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms. Furthermore, part or all of the hydrogen atoms of these groups may be substituted by an alkyl group having 1 to 10 carbon atoms, a halogen atom, a trifluoromethyl group, a cyano group, a nitro group, a hydroxyl group, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an acyloxy group having 2 to 10 carbon atoms, and part of the carbon atoms of these groups may be substituted by a carbonyl group, an ether bond, or an ester bond.

In the general formulae (d2) and (d3), specific examples of the coronium cations are the same as those mentioned above for the cations of the coronium salts represented by the general formula (1-1) described later.

In the general formula (d1), M- ^is a non-nucleophilic counter ion. Examples of the non-nucleophilic counter ions include: halogenated ions such as chloride ions and bromide ions; fluoroalkyl sulfonate ions such as trifluoromethanesulfonate ions, 1,1,1-trifluoroethanesulfonate ions, and nonafluorobutanesulfonate ions; aryl sulfonic acid ions such as toluenesulfonate ions, benzenesulfonate ions, 4-fluorobenzenesulfonate ions, and 1,2,3,4,5-pentafluorobenzenesulfonate ions; ions; alkyl sulfonate ions such as methanesulfonate ions and butanesulfonate ions; acylimidic acid ions such as bis(trifluoromethylsulfonyl)imide ions, bis(perfluoroethylsulfonyl)imide ions, bis(perfluorobutylsulfonyl)imide ions; methylated acid ions such as tris(trifluoromethylsulfonyl)methide ions and tris(perfluoroethylsulfonyl)methide ions.

The aforementioned non-nucleophilic relative ions can be further exemplified as follows: a sulfonate ion represented by the following general formula (d1-1) in which the α-position is substituted by a fluorine atom, a sulfonate ion represented by the following general formula (d1-2) in which the α-position is substituted by a fluorine atom and the β-position is substituted by a trifluoromethyl group, etc. [Chemistry 80]

In the general formula (d1-1), R ³¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and may also contain an ether bond, an ester bond, a carbonyl group, a lactone ring, or a fluorine atom. The alkyl group and the alkenyl group may be in a linear, branched, or cyclic form.

In the general formula (d1-2), R ³² is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an acyl group having 2 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, and may also contain an ether bond, an ester bond, a carbonyl group, or a lactone ring. The aforementioned alkyl group, acyl group, and alkenyl group may be in a linear, branched, or cyclic form.

Furthermore, the aforementioned Z ^2B preferably contains at least one iodine atom.

The monomers providing the repeating unit d1 may be listed as follows, but are not limited thereto. In the following formula, ^RA and ^M- are the same as those described above. [Chemical 81]

The monomers providing the repeating unit d2 may be listed as follows, but are not limited thereto. In the following formula, ^RA is the same as above. [Chemical 82]

[Chemistry 83]

[Chemistry 84]

[Chemistry 85]

[Chemistry 86]

Furthermore, the monomer providing the repeating unit d2 is preferably one having an anion as shown below. In the following formula, ^RA is the same as above. [Chemical 87]

[Chemistry 88]

[Chemistry 89]

[Chemistry 90]

[Chemistry 91]

[Chemistry 92]

[Chemistry 93]

[Chemistry 94]

The monomers providing the repeating unit d3 may be listed as follows, but are not limited thereto. In the following formula, ^RA is the same as above. [Chem. 95]

[Chemistry 96]

Repeating units d1 to d3 have the function of an acid generator. By bonding the acid generator to the polymer main chain, the acid diffusion can be reduced and the resolution reduction caused by the blurring of the acid diffusion can be prevented. In addition, the LWR will be improved by uniformly dispersing the acid generator. In addition, when using a resist material containing a repeating unit d, the admixture of the additive acid generator described later can be omitted.

In the inhibitor material of the present invention, by copolymerizing the repeating unit a having the function of a quencher of the substituted or unsubstituted iodinated monovalent aromatic carboxylic acid codon salt or iodonium salt and the repeating unit d1 to d3 having the function of an acid generator bonded to the main chain of the polymer via an ester bond, all functions can be contained in one polymer. In this case, the only materials added other than the polymer are organic solvents and surfactants, and since it is composed of simple materials, it has the advantage of high productivity.

The polymerization rate of the quencher of the coronium salt or iodonium salt of the iodonium salt of the iodonium salt of the double-bonded iodinated monovalent aromatic carboxylic acid is about the same as the polymerization rate of the acid generator of the coronium salt or iodonium salt, so the quencher and the acid generator are uniformly present in the polymer, thereby improving the edge roughness after development. When the anion part of the acid generator contains iodine, the edge roughness is further improved by utilizing the improvement of the contrast during acid generation due to the increase in the number of absorbed photons. The repeating unit a of the iodinated monovalent aromatic carboxylic acid codon or iodonium salt in the resist material of the present invention exerts the following effect: the number of absorbed photons due to the absorption of iodine increases, thereby improving the contrast of quencher decomposition and achieving improvement in edge roughness.

The aforementioned resist material may further contain a repeating unit e that does not contain an amine group but contains an iodine atom. The monomers that provide the repeating unit e may be listed as follows, but are not limited thereto. In addition, in the following formula, ^RA is the same as the aforementioned. [Chem. 97]

[Chemistry 98]

The aforementioned resist material may also contain a repeating unit f other than the aforementioned repeating unit. The repeating unit f may be selected from styrene, vinyl naphthalene, indene, acenaphthene, coumarin, coumarone, and the like.

In the above-mentioned resist material, the content ratio of the repeating units a1, a2, b1, b2, c, d1, d2, d3, e and f is preferably 0≦a1≦1.0, 0≦a2≦1.0, 0<a1+a2≦1.0, 0≦b1≦0.5, 0≦b2≦0.5, 0≦b1+b2≦0.9, 0≦c≦0.9, 0 ≦d1≦0.5, 0≦d2≦0.5, 0≦d3≦0.5, 0≦d1+d2+d3≦0.5, 0≦e≦0.5 and 0≦f≦0.5, 0.001≦a1≦0.8, 0.001≦a2≦0.8, 0.001≦a1+a2≦0.8, 0≦b1≦0.8, 0≦b2≦ 0.8, 0.1≦b1+b2≦0.8, 0≦c≦0.8, 0≦d1≦0.4, 0≦d2≦0.4, 0≦d3≦0.4, 0≦d1+d2+d3≦0.4, 0≦e≦0.4 and 0≦f≦0.4 are more preferred, and 0.005≦a1≦0.7, 0.005≦a2≦0.7, 0 .005≦a1+a2≦0.7, 0≦b1≦0.7, 0≦b2≦0.7, 0≦b1+b2≦0.7, 0≦c≦0.7, 0≦d1≦0.3, 0≦d2≦0.3, 0≦d3≦0.3, 0≦d1+d2+d3≦0.3, 0≦e≦0.3 and 0≦f≦0.3 are even better. However, a1+a2+b1+b2+c+d1+d2+d3+e+f=1.0.

When synthesizing the aforementioned resist material, for example, a monomer providing the aforementioned repeating unit is placed in an organic solvent, a free radical polymerization initiator is added, and the mixture is heated to carry out polymerization.

The organic solvents used in the polymerization include: toluene, benzene, tetrahydrofuran (THF), diethyl ether, dioxane, propylene glycol monomethyl ether, γ-butyrolactone and their mixed solvents. The polymerization initiator includes: 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(2-methylpropionic acid) dimethyl ester, benzoyl peroxide, lauryl peroxide, etc. The temperature during the polymerization is preferably 50~80℃. The reaction time is preferably 2~100 hours, and more preferably 5~20 hours.

When a monomer containing a hydroxyl group is copolymerized, the hydroxyl group can be replaced with an acetal group such as ethoxyethoxy which is easily deprotected by acid before polymerization, and then deprotected by weak acid and water after polymerization. Alternatively, the hydroxyl group can be replaced with an acetyl group, a formyl group, a trimethylacetyl group, etc. before polymerization, and then alkaline hydrolysis can be performed after polymerization.

When hydroxystyrene and hydroxyvinylnaphthalene are copolymerized, acetyloxystyrene and acetyloxyvinylnaphthalene may be used instead of hydroxystyrene and hydroxyvinylnaphthalene, and after polymerization, the acetyloxy group may be deprotected by the above-mentioned alkali hydrolysis to obtain hydroxystyrene and hydroxyvinylnaphthalene.

The alkali used in the alkali hydrolysis may be aqueous ammonia, triethylamine, etc. The reaction temperature is preferably -20 to 100°C, more preferably 0 to 60°C. The reaction time is preferably 0.2 to 100 hours, more preferably 0.5 to 20 hours.

The polystyrene-equivalent weight average molecular weight (Mw) of the resist material as measured by gel permeation chromatography (GPC) using THF as a solvent is preferably 1,000 to 500,000, more preferably 1,000 to 100,000, and even more preferably 2,000 to 30,000. If Mw is above 1,000, the resist material will have excellent heat resistance, and if it is below 500,000, it will maintain alkaline solubility and will not cause tailing after pattern formation.

In addition, when the molecular weight distribution (Mw/Mn) of the aforementioned resist material is wide, there are concerns that foreign matter may be observed on the pattern after exposure or the shape of the pattern may deteriorate due to the presence of low molecular weight and high molecular weight polymers. As the pattern rules become finer, the influence of Mw and Mw/Mn is also likely to become greater. Therefore, in order to obtain a resist material suitable for use in fine pattern sizes, the Mw/Mn of the aforementioned resist material is preferably 1.0~2.0, and a narrow distribution of 1.0~1.5 is particularly preferred.

In order to obtain a narrowly dispersed polymer, not only conventional free radical polymerization but also living free radical polymerization can be used. Examples of living free radical polymerization include: living free radical polymerization using nitroxide free radicals (Nitroxide-Mediated radical Polymerization: NMP), atom transfer radical polymerization (Atom Transfer Radical Polymerization: ATRP), and reversible addition-fragmentation chain transfer (Reversible Addition-Fragmentation chain Transfer: RAFT) polymerization.

The above-mentioned resist material may also include two or more polymers having different composition ratios, Mw, and Mw/Mn. In addition, a polymer containing repeating units a and a polymer not containing repeating units a may be mixed.

[Resistant composition] In addition, the present invention provides a resist composition, which is a resist composition containing the resist material described above. The resist composition of the present invention preferably further contains one or more selected from a photoacid generator, an organic solvent, a quencher, and a surfactant. The following describes the components contained in the resist composition.

[Acid Generator] The resist material of the present invention may further contain an acid generator that generates a strong acid (hereinafter also referred to as an additive acid generator). The strong acid referred to herein refers to a compound having an acidity sufficient to cause a deprotection reaction of the acid-labile group of the resist material. Examples of the aforementioned acid generator include compounds that are sensitive to active light or radiation and generate an acid (photoacid generator). If the photoacid generator is a compound that generates an acid due to irradiation with high-energy radiation, it may be any compound, and preferably one that generates a sulfonic acid, an imidic acid, or a methylated acid. Ideal photoacid generators include: cobalt salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, oxime-O-sulfonate type acid generators, etc. Specific examples of photoacid generators include those described in paragraphs [0122] to [0142] of Japanese Patent Publication No. 2008-111103.

Furthermore, the photoacid generator may also preferably be a cobalt salt represented by the following general formula (1-1) or an iodine salt represented by the following general formula (1-2).

In the general formulae (1-1) and (1-2), ^R101 to ^R105 are independently monovalent hydrocarbon groups having 1 to 20 carbon atoms which may contain impurity atoms. In addition, any two of ^R101 , ^R102 and ^R103 may be bonded to each other and form a ring together with the sulfur atom to which they are bonded. The monovalent hydrocarbon group may be in the form of a straight chain, a branched structure or a ring, and specific examples thereof are the same as those mentioned above.

In the general formulae (1-1) and (1-2), X- ^is an anion selected from the following general formulae (1A) to (1D).

In the general formula (1A), R ^fa is a fluorine atom or a carbon group having 1 to 40 carbon atoms which may contain a heteroatom. The aforementioned carbon group may be saturated or unsaturated, and may be in a linear, branched, or cyclic form. Specific examples thereof include the same examples as those described below as the carbon group represented by R ¹⁰⁷ in the general formula (1A').

The anion represented by the general formula (1A) is preferably represented by the following general formula (1A').

In the general formula (1A'), ^R106 is a hydrogen atom or a trifluoromethyl group, preferably a trifluoromethyl group. ^R107 is a carbon number 1-38 alkyl group which may contain a heteroatom. The heteroatom is preferably an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, etc., more preferably an oxygen atom. The carbon number 6-30 is particularly preferred from the viewpoint of obtaining a high resolution when forming a fine pattern.

The alkyl group represented by R ¹⁰⁷ may be saturated or unsaturated, and may be in the form of a linear chain, a branched chain, or a ring. Specific examples thereof include: alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, dibutyl, tertiary butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecyl, eicosyl, etc.; cyclic saturated alkyl groups such as cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, norbornyl, norbornylmethyl, tricyclodecyl, tetracyclododecyl, tetracyclododecylmethyl, dicyclohexylmethyl, etc.; unsaturated alkyl groups such as allyl and 3-cyclohexenyl, aryl groups such as phenyl, 1-naphthyl, 2-naphthyl, etc.; aralkyl groups such as benzyl and diphenylmethyl, etc., etc.

Furthermore, part or all of the hydrogen atoms of these groups may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and part of the carbon atoms of these groups may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms, and as a result, hydroxyl groups, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate groups, lactone rings, sultone rings, carboxylic anhydrides, halogen groups, and the like may be contained. Examples of heteroatoms-containing alkyl groups include tetrahydrofuranyl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamidomethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetyloxymethyl, 2-carboxy-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl, and 3-oxocyclohexyl.

The synthesis of the cobalt salt containing an anion represented by the general formula (1A') is described in Japanese Unexamined Patent Publication No. 2007-145797, Japanese Unexamined Patent Publication No. 2008-106045, Japanese Unexamined Patent Publication No. 2009-007327, Japanese Unexamined Patent Publication No. 2009-258695, etc. In addition, the cobalt salts described in Japanese Unexamined Patent Publication No. 2010-215608, Japanese Unexamined Patent Publication No. 2012-041320, Japanese Unexamined Patent Publication No. 2012-106986, Japanese Unexamined Patent Publication No. 2012-153644, etc. can also be preferably used.

Examples of the anions represented by the general formula (1A) include the same examples as those exemplified as the anions represented by the formula (1A) in Japanese Unexamined Patent Application Publication No. 2018-197853.

In the general formula (1B), ^Rfb1 and ^Rfb2 are each independently a fluorine atom or a alkyl group having 1 to 40 carbon atoms which may contain impurities. The aforementioned alkyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include the same examples as those exemplified in the description of ^R107 in the general formula (1A'). ^Rfb1 and ^Rfb2 are preferably fluorine atoms or linear fluorinated alkyl groups having 1 to 4 carbon atoms. Furthermore, ^Rfb1 and ^Rfb2 may be bonded to each other and form a ring together with the group to which they are bonded ( _-CF2 - _SO2 -N ^-- _SO2 - _CF2- ), in which case the group obtained by bonding ^Rfb1 and ^Rfb2 to each other is preferably a fluorinated ethyl group or a fluorinated propyl group.

In the general formula (1C), ^Rfc1 , ^Rfc2 and ^Rfc3 are independently fluorine atoms or alkyl groups having 1 to 40 carbon atoms which may contain impurities. The aforementioned alkyl groups may be saturated or unsaturated, and may be linear, branched or cyclic. Specific examples thereof include the same examples as those exemplified in the description of ^R107 in the general formula (1A'). ^Rfc1 , ^Rfc2 and ^Rfc3 are preferably fluorine atoms or linear fluorinated alkyl groups having 1 to 4 carbon atoms. Furthermore, ^Rfc1 and ^Rfc2 may bond to each other and form a ring together with the group to which they bond ( _-CF2 - _SO2 -C ^-- _SO2 - _CF2- ). In this case, the group obtained by bonding ^Rfc1 and ^Rfc2 to each other is preferably a fluorinated ethyl group or a fluorinated propyl group.

In the general formula (1D), ^Rfd is a alkyl group having 1 to 40 carbon atoms which may contain a heteroatom. The alkyl group may be saturated or unsaturated and may be linear, branched or cyclic. Specific examples thereof include the same examples as those exemplified in the description of ^R107 in the general formula (1A').

The synthesis of the cobalt salt containing the anion represented by the general formula (1D) is described in detail in Japanese Unexamined Patent Publication Nos. 2010-215608 and 2014-133723.

Examples of the anions represented by the general formula (1D) include the same examples as those exemplified as the anions represented by the formula (1D) in Japanese Unexamined Patent Application Publication No. 2018-197853.

In addition, the photoacid generator containing the anion represented by the general formula (1D) has no fluorine at the α-position of the sulfonic group, but has two trifluoromethyl groups at the β-position, and thus has acidity sufficient to cut off the acid-unstable group in the resist material. Therefore, it can be used as a photoacid generator.

In addition, the photoacid generator represented by the following general formula (2) can also be preferably used.

In the general formula (2), ^R201 and ^R202 are each independently a alkyl group having 1 to 30 carbon atoms which may contain a heteroatom. ^R203 may be an alkylene group having 1 to 30 carbon atoms which may contain a heteroatom. In addition, ^R201 and ^R202 or ^R201 and ^R203 may be bonded to each other and form a ring together with the sulfur atom to which they are bonded. In this case, the aforementioned ring may be exemplified as the ring which can be formed when ^R101 and ^R102 are bonded to each other and together with the sulfur atom to which they are bonded in the description of the general formula (1-1).

The alkyl group represented by R ²⁰¹ and R ²⁰² may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, dibutyl, tertiary butyl, n-pentyl, tertiary pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, tricyclo[5.2.1.0 ^2,6 ] cyclic saturated alkyl groups such as decyl and adamantyl; aryl groups such as phenyl, tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, di-butylphenyl, tertiary butylphenyl, naphthyl, methyl naphthyl, ethyl naphthyl, n-propyl naphthyl, isopropyl naphthyl, n-butyl naphthyl, isobutyl naphthyl, di-butyl naphthyl, tertiary butyl naphthyl, anthracenyl, etc. In addition, part or all of the hydrogen atoms of these groups may be substituted by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and part of the carbon atoms of these groups may be substituted by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms, and as a result, hydroxyl groups, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate groups, lactone rings, sultone rings, carboxylic anhydrides, halogenalkyl groups, etc. may be contained.

The alkylene group represented by R ²⁰³ may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include: methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptane-1,17-diyl, alkylene groups such as cyclopentanediyl, cyclohexanediyl, norbornanediyl and adamantanediyl; arylene groups such as phenylene, methylphenylene, ethylphenylene, n-propylphenylene, isopropylphenylene, n-butylphenylene, isobutylphenylene, di-butylphenylene, tertiary butylphenylene, naphthyl, methylnaphthyl, ethylnaphthyl, n-propylnaphthyl, isopropylnaphthyl, n-butylnaphthyl, isobutylnaphthyl, di-butylnaphthyl and tertiary butylnaphthyl; and the like. Furthermore, part or all of the hydrogen atoms of these groups may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and part of the carbon atoms of these groups may be replaced by groups containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms, and as a result, hydroxyl groups, cyano groups, carbonyl groups, ether bonds, ester bonds, sulfonate bonds, carbonate groups, lactone rings, sultone rings, carboxylic anhydrides, halogenated groups, etc. are contained. The heteroatoms are preferably oxygen atoms.

In the general formula (2), ^L1 is a single bond, an ether bond, or an alkylene group having 1 to 20 carbon atoms which may contain heteroatoms. The alkylene group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof may be the same as those for the alkylene group represented by ^R203 .

In the general formula (2), ^XA , ^XB , ^XC and ^XD are independently a hydrogen atom, a fluorine atom or a trifluoromethyl group. However, at least one of ^XA , ^XB , ^XC and ^XD is a fluorine atom or a trifluoromethyl group.

In general formula (2), k is an integer between 0 and 3.

The photoacid generator represented by the general formula (2) is preferably represented by the following general formula (2').

In the general formula (2'), ^L1 is the same as described above. ^RHF is a hydrogen atom or a trifluoromethyl group, preferably a trifluoromethyl group. ^R301 , ^R302 and ^R303 are each independently a hydrogen atom or a carbonyl group having 1 to 20 carbon atoms which may contain a heteroatom. The aforementioned carbonyl group may be saturated or unsaturated, and may be in the form of a straight chain, a branched chain or a ring. Specific examples thereof may be the same as those exemplified in the description of ^R107 in the general formula (1A'). x and y are each independently an integer of 0 to 5, and z is an integer of 0 to 4.

Examples of the photoacid generator represented by the general formula (2) include the same examples as those exemplified as the photoacid generator represented by the formula (2) in Japanese Unexamined Patent Application Publication No. 2017-026980.

Among the above-mentioned photoacid generators, those containing anions represented by general formula (1A') or (1D) are particularly preferred because they have low acid diffusion and excellent solubility in the inhibitor solvent. Also, those represented by general formula (2') are particularly preferred because they have extremely low acid diffusion.

In addition, the photoacid generator may also be a cobalt salt or an iodine salt having an anion containing an aromatic ring substituted with an iodine atom or a bromine atom. Such salts may be those represented by the following general formula (3-1) or (3-2). [Chemical 104]

In general formulas (3-1) and (3-2), p is an integer satisfying 1≦p≦3. q and r are integers satisfying 1≦q≦5, 0≦r≦3, and 1≦q+r≦5. q is preferably an integer satisfying 1≦q≦3, more preferably 2 or 3. r is preferably an integer satisfying 0≦r≦2.

In the general formulae (3-1) and (3-2), ^XBI is an iodine atom or a bromine atom, and when q is 2 or more, they may be the same or different from each other.

In the general formulae (3-1) and (3-2), L ¹¹ is a single bond, an ether bond, an ester bond, or a saturated alkylene group having 1 to 6 carbon atoms which may contain an ether bond or an ester bond. The saturated alkylene group may be linear, branched, or cyclic.

In the general formulae (3-1) and (3-2), ^L12 is a single bond or a divalent linking group having 1 to 20 carbon atoms when r is 1, and is a trivalent or tetravalent linking group having 1 to 20 carbon atoms when r is 2 or 3. The linking group may contain an oxygen atom, a sulfur atom or a nitrogen atom.

In the general formulae (3-1) and (3-2), R ⁴⁰¹ is a hydroxyl group, a carboxyl group, a fluorine atom, a chlorine atom, a bromine atom or an amino group, or a saturated alkyl group having 1 to 20 carbon atoms, a saturated alkyloxy group having 1 to 20 carbon atoms, a saturated alkyloxycarbonyl group having 2 to 10 carbon atoms, a saturated alkylcarbonyloxy group having 2 to 20 carbon atoms or a saturated alkylsulfonyloxy group having 1 to 20 carbon atoms which may contain a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, an amino group or an ether bond, or -NR ^401A -C(=O)-R ^401B or -NR ^401A -C(=O)-OR ^401B . R ^401A is a hydrogen atom or a saturated alkyl group having 1 to 6 carbon atoms, and may contain a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a saturated alkylcarbonyl group having 2 to 6 carbon atoms, or a saturated alkylcarbonyloxy group having 2 to 6 carbon atoms. R ^401B is an aliphatic alkyl group having 1 to 16 carbon atoms or an aryl group having 6 to 12 carbon atoms, and may contain a halogen atom, a hydroxyl group, a saturated alkyloxy group having 1 to 6 carbon atoms, a saturated alkylcarbonyl group having 2 to 6 carbon atoms, or a saturated alkylcarbonyloxy group having 2 to 6 carbon atoms. The aforementioned aliphatic alkyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. The aforementioned saturated alkyl group, saturated alkyloxy group, saturated alkyloxycarbonyl group, saturated alkylcarbonyl group and saturated alkylcarbonyloxy group may be linear, branched or cyclic. When p and/or r is 2 or more, each R ⁴⁰¹ may be the same or different.

Among them, R ⁴⁰¹ is preferably a hydroxy group, -NR ^401A -C(=O)-R ^401B , -NR ^401A -C(=O)-OR ^401B , a fluorine atom, a chlorine atom, a bromine atom, a methyl group, a methoxy group or the like.

In general formulae (3-1) and (3-2), ^Rf11 to ^Rf14 are independently hydrogen atoms, fluorine atoms or trifluoromethyl groups, but at least one of them is a fluorine atom or a trifluoromethyl group. In addition, ^Rf11 and ^Rf12 may be combined to form a carbonyl group. It is particularly preferred that ^{both Rf13} and ^Rf14 are fluorine atoms.

In the general formulae (3-1) and (3-2), ^R402 , ^R403 , ^R404 , ^R405 and ^R406 are independently fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, or carbonyl groups having 1 to 20 carbon atoms which may contain impurities. The aforementioned carbonyl groups may be saturated or unsaturated, and may be linear, branched or cyclic. Specific examples thereof are the same as those exemplified as the carbonyl groups represented by ^R101 to ^R105 in the description of the general formulae (1-1) and (1-2). Furthermore, part or all of the hydrogen atoms of these groups may be substituted by hydroxyl groups, carboxyl groups, halogen atoms, cyano groups, nitro groups, hydroxyl groups, sultone groups, sulfonyl groups or groups containing sulphur salts, and part of the carbon atoms of these groups may be substituted by ether bonds, ester bonds, carbonyl groups, amide bonds, carbonate groups or sulfonate bonds. Furthermore, ^R402 and ^R403 may be bonded to each other and to form a ring together with the sulfur atom to which they are bonded. In this case, the aforementioned rings may be exemplified by the same examples as those exemplified in the description of the general formula (1-1) as the ring that can be formed when ^R101 and ^R102 are bonded to each other and to the sulfur atom to which they are bonded.

Examples of the cations of the coronium salts represented by the general formula (3-1) include the same examples as those given for the cations of the coronium salts represented by the general formula (1-1). Examples of the cations of the iodonium salts represented by the general formula (3-2) include the same examples as those given for the cations of the iodonium salts represented by the general formula (1-2).

The anion of the onium salt represented by the general formula (3-1) or (3-2) can be listed as follows, but is not limited thereto. In the following formula, ^XBI is the same as above. [Chemical 105]

[Chemistry 106]

[Chemistry 107]

[Chemistry 108]

[Chemistry 109]

[Chemistry 110]

[Chemistry 111]

[Chemistry 112]

[Chemistry 113]

[Chemistry 114]

[Chemistry 115]

[Chemistry 116]

[Chemistry 117]

[Chemistry 118]

[Chemistry 119]

[Chemistry 120]

[Chemistry 121]

[Chemistry 122]

[Chemistry 123]

[Chemistry 124]

[Chemistry 125]

[Chemistry 126]

[Chemistry 127]

In the resistor composition of the present invention, the content of the additive acid generator is preferably 0.1 to 50 parts by mass, and more preferably 1 to 40 parts by mass relative to 100 parts by mass of the resistor material. The above-mentioned resistor material contains repeating units d1 to d3 and/or contains an additive acid generator, whereby the resistor composition of the present invention can function as a chemically amplified resistor composition.

[Organic solvent] The inhibitor composition of the present invention may also contain an organic solvent. The aforementioned organic solvent is not particularly limited as long as it can dissolve the aforementioned components and the components described below. Such organic solvents include: ketones such as cyclohexanone, cyclopentanone, methyl-2-n-pentyl ketone, and 2-heptanone described in paragraphs [0144] to [0145] of Japanese Patent Publication No. 2008-111103; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; propylene glycol monomethyl ether, ethylene glycol monomethyl ether, and 1-methoxy-2-propanol; Ethers such as propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tertiary butyl acetate, tertiary butyl propionate, and propylene glycol monotertiary butyl ether acetate; lactones such as γ-butyrolactone; and their mixed solvents.

In the resist composition of the present invention, the content of the organic solvent is preferably 100-10,000 parts by mass, more preferably 200-8,000 parts by mass, relative to 100 parts by mass of the resist material.

[Other components] In addition to the aforementioned components, surfactants, dissolution inhibitors, etc. are appropriately combined and mixed according to the purpose to form a resist composition. In the exposure part, the aforementioned resist material will accelerate its dissolution rate in the developer due to the catalytic reaction, so a highly sensitive resist composition can be made. At this time, the resist film has high dissolution contrast and resolution, has exposure tolerance, excellent process adaptability, and good pattern shape after exposure. At the same time, it can especially inhibit acid diffusion, so the density difference is small. Considering these characteristics, it can be made into a highly practical and very effective resist material for ultra-large integrated circuits.

The aforementioned surfactants can be listed in paragraphs [0165] to [0166] of Japanese Patent Publication No. 2008-111103. By adding a surfactant, the coating property of the resist composition can be further improved or controlled. The surfactant can be used alone or in combination of two or more. In the resist composition of the present invention, the content of the aforementioned surfactant is preferably 0.0001 to 10 parts by mass relative to 100 parts by mass of the resist material.

By adding a dissolution inhibitor, the difference in dissolution rate between the exposed area and the unexposed area can be further increased, and the resolution can be further improved.

The dissolution inhibitor preferably has a molecular weight of 100 to 1,000, more preferably 150 to 800, and may include compounds containing two or more phenolic hydroxyl groups in the molecule, wherein the hydrogen atoms of the phenolic hydroxyl groups are replaced by acid-labile groups at a ratio of 0 to 100 mol % as a whole, or compounds containing carboxyl groups in the molecule, wherein the hydrogen atoms of the carboxyl groups are replaced by acid-labile groups at a ratio of 50 to 100 mol % as a whole. Specific examples include: compounds in which the hydrogen atoms of the hydroxyl and carboxyl groups of bisphenol A, phenolphthalein, cresol novolac resin, naphthyl carboxylic acid, adamantane carboxylic acid, and cholic acid are replaced by acid-labile groups, such as those described in paragraphs [0155] to [0178] of Japanese Patent Application Laid-Open No. 2008-122932.

The content of the dissolution inhibitor is preferably 0 to 50 parts by mass, more preferably 5 to 40 parts by mass, relative to 100 parts by mass of the resist material. The dissolution inhibitor may be used alone or in combination of two or more.

The inhibitor composition of the present invention may also be mixed with a quencher (hereinafter referred to as other quenchers). The aforementioned other quenchers may include conventional alkaline compounds. Conventional alkaline compounds include: primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds with carboxyl groups, nitrogen-containing compounds with sulfonyl groups, nitrogen-containing compounds with hydroxyl groups, nitrogen-containing compounds with hydroxyphenyl groups, alcoholic nitrogen-containing compounds, amides, imides, carbamates, etc. In particular, the primary, secondary, and tertiary amine compounds described in paragraphs [0146] to [0164] of Japanese Patent Publication No. 2008-111103 are preferred, and amine compounds having a hydroxyl group, an ether bond, an ester bond, a lactone ring, a cyano group, or a sulfonate bond, or compounds having a carbamate group described in Japanese Patent Publication No. 3790649 are particularly preferred. By adding such alkaline compounds, for example, the diffusion rate of the acid in the resist film can be further suppressed or the shape can be corrected.

In addition, other quenching agents include onium salts such as coronium salts, iodonium salts, and ammonium salts of sulfonic acids and carboxylic acids that are not fluorinated at the α-position as described in Japanese Patent Application Laid-Open No. 2008-158339. Sulfonic acids, imidic acids, or methide acids that are fluorinated at the α-position are necessary for deprotecting the acid labile group of carboxylic acid esters, and by salt exchange with onium salts that are not fluorinated at the α-position, sulfonic acids or carboxylic acids that are not fluorinated at the α-position are released. Sulfonic acids and carboxylic acids that are not fluorinated at the α-position do not cause deprotection reactions, and therefore function as quenching agents.

Other quenchers include polymer quenchers described in Japanese Patent Application Publication No. 2008-239918. The polymer quencher improves the rectangularity of the patterned resist by being aligned on the resist surface after coating. The polymer quencher also has the effect of preventing film loss and doming of the pattern when using a protective film for immersion exposure.

In the resistor composition of the present invention, the content of other quenchers is preferably 0-5 parts by weight, more preferably 0-4 parts by weight, relative to 100 parts by weight of the resistor material. Other quenchers may be used alone or in combination of two or more.

The resist composition of the present invention may also be mixed with a water-repellent improver for improving the water-repellency of the resist surface after spin coating. The water-repellent improver can be used in immersion lithography without using a top coat. The water-repellent improver is preferably a polymer compound containing a fluorinated alkyl group, a polymer compound containing a 1,1,1,3,3,3-hexafluoro-2-propanol residue of a specific structure, and is preferably exemplified in Japanese Patent Publication No. 2007-297590 and Japanese Patent Publication No. 2008-111103. The water-repellent improver needs to be dissolved in an organic solvent developer. The aforementioned specific hydrophobicity improver having a 1,1,1,3,3,3-hexafluoro-2-propanol residue has good solubility in developer. As for the hydrophobicity improver, a polymer compound containing repeating units containing an amine group or an amine salt has a high effect of preventing the evaporation of the acid during post-exposure baking (PEB) and preventing the poor opening of the hole pattern after development. The hydrophobicity improver can be used alone or in combination of two or more. In the resist composition of the present invention, the content of the hydrophobicity improver is preferably 0 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the resist material.

The resist composition of the present invention may also contain acetylene alcohols. Examples of the acetylene alcohols include those described in paragraphs [0179] to [0182] of Japanese Patent Publication No. 2008-122932. In the resist composition of the present invention, the content of the acetylene alcohols is preferably 0 to 5 parts by weight relative to 100 parts by weight of the resist material.

[Pattern Formation Method] When the resist composition of the present invention is used in the manufacture of various integrated circuits, known lithography techniques can be applied. That is, the present invention provides a pattern formation method, comprising the following steps: Using the resist composition described above to form a resist film on a substrate, Exposing the resist film to high-energy radiation, and Developing the exposed resist film using a developer.

For example, the resist composition of the present invention is applied to a substrate (Si, SiO 2 , SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflection film, etc.) for manufacturing integrated circuits or a substrate (Cr, CrO, CrON, MoSi ₂ , SiO ₂ , etc.) for manufacturing mask circuits by a suitable coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, or scraping coating to a coating thickness of 0.01 to ₂ μm. The resist composition is pre-baked on a heating plate preferably at 60 to 150° C. for 10 seconds to 30 minutes, and more preferably at 80 to 120° C. for 30 seconds to 20 minutes, to form a resist film.

Then, the resist film is exposed using high-energy radiation. Examples of the high-energy radiation include ultraviolet radiation, far ultraviolet radiation, EB (electron beam), EUV (extreme ultraviolet radiation), X-rays, soft X-rays, excimer lasers, i-rays, gamma rays, synchrotron radiation, etc. Among them, i-rays, KrF excimer lasers, ArF excimer lasers, electron beams, or extreme ultraviolet radiation with a wavelength of 3 to 15 nm are preferably used. When ultraviolet radiation, far ultraviolet radiation, EUV, X-rays, soft X-rays, excimer lasers, gamma rays, synchrotron radiation, etc. are used as the high-energy radiation, a mask for forming the intended pattern is used, and the exposure is preferably about 1 to 200 mJ/cm ² and more preferably about 10 to 100 mJ/cm ² . When EB is used as high-energy radiation, the exposure is preferably about 0.1-100 μC/cm ² and more preferably about 0.5-50 μC/cm ² , either directly or using a mask for forming a desired pattern. In addition, the resist composition of the present invention is particularly suitable for fine patterning using KrF excimer laser, ArF excimer laser, EB, EUV, X-ray, soft X-ray, gamma ray, synchrotron radiation among high-energy radiation, and is particularly suitable for fine patterning using EB or EUV.

After the exposure, PEB may be performed on a heating plate preferably at 50-150° C. for 10 seconds to 30 minutes, more preferably at 60-120° C. for 30 seconds to 20 minutes.

After exposure or PEB, a developer containing 0.1-10 mass % and preferably 2-5 mass % of an alkaline aqueous solution of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH) or the like is used, and developed by a common method such as a dip method, a puddle method, or a spray method for 3 seconds to 3 minutes and preferably 5 seconds to 2 minutes, whereby the portion irradiated with light is dissolved in the developer, while the portion not exposed is not dissolved, and a desired positive pattern is formed on the substrate.

It is also possible to use a resist composition containing a resist material containing an acid-unstable group and to develop with an organic solvent to obtain a negative development of a negative pattern. The developer used in this case can be exemplified by: 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methyl cyclohexanone, acetophenone, methyl acetophenone, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, butyl acetate, isoamyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl valerate, methyl pentenoate, methyl crotonate, crotonate, propyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl valerate, methyl pentenoate, methyl crotonate, propyl ... The organic solvents include ethyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, 2-phenylethyl acetate, and the like. These organic solvents may be used alone or in combination of two or more.

When the development is finished, rinsing can be performed. The rinsing liquid is preferably a solvent that is miscible with the developer and does not dissolve the resist film. Such solvents can ideally be alcohols with 3 to 10 carbon atoms, ether compounds with 8 to 12 carbon atoms, alkanes, alkenes, alkynes with 6 to 12 carbon atoms, and aromatic solvents.

Specifically, alcohols having 3 to 10 carbon atoms include n-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tertiary butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, tertiary butyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3 -dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, 1-octanol, etc.

Ether compounds with carbon numbers of 8 to 12 can be listed as: di-n-butyl ether, di-isobutyl ether, di(dibutyl) ether, di-n-pentyl ether, di-isopentyl ether, di(dipentyl) ether, di(tertiary amyl) ether, di-n-hexyl ether, etc.

Alkanes with carbon numbers of 6 to 12 include hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, cyclooctane, cyclononane, etc. Alkenes with carbon numbers of 6 to 12 include hexene, heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene, cycloheptene, cyclooctene, etc. Alkynes with carbon numbers of 6 to 12 include hexyne, heptyne, octyne, etc.

Aromatic solvents include toluene, xylene, ethylbenzene, isopropylbenzene, tert-butylbenzene, mesitylene, etc.

By performing rinsing, the occurrence of resist pattern collapse and defects can be reduced. In addition, rinsing is not necessary, and the amount of solvent used can be reduced by not performing rinsing.

The hole pattern and trench pattern after development can also be shrunk by heat flow, RELACS technology or DSA technology. A shrinking agent is applied on the hole pattern, and the diffusion of the acid catalyst from the resist layer during baking will cause cross-linking of the shrinking agent on the surface of the resist, and the shrinking agent will adhere to the side wall of the hole pattern. The baking temperature is preferably 70~180℃, preferably 80~170℃, and the time is preferably 10~300 seconds to remove the excess shrinking agent and shrink the hole pattern. [Example]

Hereinafter, the present invention will be specifically described with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples.

[1]Synthesis of monomer [Synthesis example] [Synthesis example 1-1]Synthesis of monomer 1 Monomer 1 was synthesized according to the following process.

(1) Synthesis of Compound 2 Compound 1 (580 g), 2-chloroethanol (520 g), potassium carbonate (726 g), sodium bromide (31.5 g), and DMF (3,970 g) were mixed and stirred at 90°C for 20 hours. After the reaction was completed, the mixture was ice-cooled, pure water (3,600 g) was added, and the mixture was stirred for 30 minutes. Methyl isobutyl ketone (4,500 g) was then added, and the mixture was stirred for 1 hour. After the organic layer was separated and extracted, a conventional aqueous work-up was performed, the solvent was distilled off, hexane (3,500 g) was added, the mixture was stirred for 2 hours, and then filtered to obtain Compound 2 (604 g) as a solid. The ¹ H-NMR (500 MHz, DMSO-d ₆ ) spectrum of compound 2 is shown in Figure 1.

(2) Synthesis of Compound 3 Compound 2 (600 g) and tetrahydrofuran (2,800 g) were stirred under ice-cooling, and a 25% sodium hydroxide aqueous solution (330 g) and pure water (900 g) were added dropwise. The mixture was stirred at 40°C for 16 hours. After the reaction was completed, the organic solvent was distilled off and the aqueous solution was washed with TBME. 20% hydrochloric acid (430 g) and hexane (1 L) were added and stirred for crystallization, followed by filtration to obtain Compound 3 (560 g) in solid form. ^{The 1} H-NMR (500 MHz, DMSO-d ₆ ) spectrum of Compound 3 is shown in Figure 2. [Chemical 129]

(3) Synthesis of Compound 4 Compound 3 (560 g), methacrylic anhydride (340 g), acetonitrile (3,000 g), and a polymerization inhibitor (1,000 ppm/theoretical yield) were dissolved, and a mixture of triethylamine (442 g), DMAP (22 g), and acetonitrile (600 g) was added dropwise under ice-cooling, followed by stirring for 3 hours under ice-cooling. After the reaction was completed, 5% sodium bicarbonate water (1,900 g) was added under ice-cooling, and after stirring for 20 minutes, 20% hydrochloric acid aqueous solution (1,070 g) and pure water (5,300 g) were added and stirred for crystallization. The obtained solid was dissolved in ethyl acetate (4,500 g) by filtration, and the organic layer was separated and extracted, and then washed with saturated saline and pure water, and the organic layer was treated with activated carbon. The solvent was distilled off, hexane (5.7 L) was added, and the mixture was stirred for crystallization and filtered to obtain compound 4 (460 g) in a solid form. ^{The 1} H-NMR (500 MHz, DMSO-d ₆ ) spectrum of compound 4 is shown in FIG3 . [Chemical 130]

(4) Synthesis of Monomer 1 Potassium carbonate (17 g), 1-pentanol (40 g), and pure water (90 g) were added to compound 4 (38 g) and stirred at room temperature for 1 hour. Compound 5 (44 g) and dichloromethane (300 g) were then added and stirred for 2 hours. After separation and extraction of the organic layer, a conventional aqueous work-up was performed, a polymerization inhibitor (100 ppm/theoretical yield) was added, and the solvent was distilled off to obtain monomer 1 (60 g) in an oily form. The obtained monomer 1 was dissolved in γ-butyrolactone (56 g) to prepare a γ-butyrolactone solution. ^{The 1} H-NMR (500 MHz, DMSO-d ₆ ) spectrum of monomer 1 is shown in FIG4 . In addition to the target peak, the solvent peaks used (1-pentanol, methyl isobutyl ketone, γ-butyrolactone) were also detected.

By ion exchange between coronium salt bromide and iodinated benzoic acid compounds or benzoic acid compounds having a polymerizable double bond, the following monomers 2 to 15 and comparative monomers 1 to 3 were obtained. Monomer 1 is also shown together.

[Chemistry 132]

[Chemistry 133]

[Chemistry 134]

[Chemistry 135]

[2] Synthesis of polymers The acid-labile monomer (ALG monomer 1) and PAG monomers 1 to 8 used in the synthesis of polymers are as follows. The Mw of the polymers is a polystyrene-converted value measured by GPC using THF as a solvent. [Chem. 136]

[Chemistry 137]

[Chemistry 138]

[Synthesis Example 2-1] Synthesis of Polymer 1 In a 2L flask, monomer 1 (3.5g), 1-methyl-1-cyclopentyl methacrylate (8.4g), 4-hydroxystyrene (5.4g), and THF (40g) as a solvent were added. The reaction vessel was cooled to -70°C in a nitrogen environment, and the decompression, degassing and nitrogen blowing were repeated 3 times. After the temperature was raised to room temperature, AIBN (1.2g) as a polymerization initiator was added, the temperature was raised to 60°C, and it was reacted for 15 hours. The reaction solution was added to 1L of isopropanol, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer 1. The composition of polymer 1 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC.

[Synthesis Example 2-2] Synthesis of Polymer 2: In a 2L flask, monomer 2 (3.4g), 1-methyl-1-cyclohexyl methacrylate (7.3g), 4-hydroxystyrene (4.8g), PAG monomer 2 (11.0g), and THF (40g) as a solvent were added. The reaction vessel was cooled to -70°C in a nitrogen environment, and the decompression, degassing and nitrogen blowing were repeated 3 times. After the temperature was raised to room temperature, AIBN (1.2g) as a polymerization initiator was added, the temperature was raised to 60°C, and it was reacted for 15 hours. The reaction solution was added to 1L of isopropanol, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer 2. The composition of polymer 2 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC.

[Synthesis Example 2-3] Synthesis of polymer 3: In a 2L flask, monomer 3 (3.0g), 1-methyl-1-cyclopentyl methacrylate (8.4g), 4-hydroxystyrene (3.6g), PAG monomer 1 (11.9g), and THF (40g) as a solvent were added. The reaction vessel was cooled to -70°C in a nitrogen environment, and the decompression, degassing and nitrogen blowing were repeated 3 times. After the temperature was raised to room temperature, AIBN (1.2g) as a polymerization initiator was added, the temperature was raised to 60°C, and the reaction was allowed to proceed for 15 hours. The reaction solution was added to 1L of isopropanol, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer 3. The composition of polymer 3 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC.

[Synthesis Example 2-4] Synthesis of polymer 4: In a 2L flask, monomer 4 (3.2g), 1-methyl-1-cyclopentyl methacrylate (8.4g), 3-hydroxystyrene (3.6g), PAG monomer 2 (11.0g), and THF (40g) as a solvent were added. The reaction vessel was cooled to -70°C in a nitrogen environment, and the decompression, degassing and nitrogen blowing were repeated 3 times. After the temperature was raised to room temperature, AIBN (1.2g) as a polymerization initiator was added, the temperature was raised to 60°C, and the reaction was allowed to proceed for 15 hours. The reaction solution was added to 1L of isopropanol, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer 4. The composition of polymer 4 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC.

[Synthesis Example 2-5] Synthesis of polymer 5: In a 2L flask, monomer 5 (4.1g), 1-methyl-1-cyclopentyl methacrylate (8.4g), 4-hydroxystyrene (4.2g), PAG monomer 3 (8.5g), and THF (40g) as a solvent were added. The reaction container was cooled to -70°C in a nitrogen environment, and the decompression, degassing and nitrogen blowing were repeated 3 times. After the temperature was raised to room temperature, AIBN (1.2g) as a polymerization initiator was added, the temperature was raised to 60°C, and it was reacted for 15 hours. The reaction solution was added to 1L of isopropanol, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer 5. The composition of polymer 5 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC.

[Synthesis Example 2-6] Synthesis of polymer 6: In a 2L flask, monomer 6 (4.9g), ALG monomer 1 (8.9g), 4-hydroxystyrene (5.4g), PAG monomer 4 (10.2g), and THF (40g) as a solvent were added. The reaction vessel was cooled to -70°C in a nitrogen environment, and the decompression, degassing and nitrogen blowing were repeated 3 times. After the temperature was raised to room temperature, AIBN (1.2g) as a polymerization initiator was added, the temperature was raised to 60°C, and it was reacted for 15 hours. The reaction solution was added to 1L of isopropanol, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer 6. The composition of polymer 6 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC.

[Synthesis Example 2-7] Synthesis of polymer 7: In a 2L flask, monomer 7 (3.8g), 1-methyl-1-cyclopentyl methacrylate (8.4g), 4-hydroxystyrene (4.8g), PAG monomer 5 (5.5g), and THF (40g) as a solvent were added. The reaction vessel was cooled to -70°C in a nitrogen environment, and the decompression, degassing and nitrogen blowing were repeated 3 times. After the temperature was raised to room temperature, AIBN (1.2g) as a polymerization initiator was added, the temperature was raised to 60°C, and the reaction was allowed to proceed for 15 hours. The reaction solution was added to 1L of isopropanol, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer 7. The composition of polymer 7 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC.

[Synthesis Example 2-8] Synthesis of polymer 8: In a 2L flask, monomer 8 (3.4g), ALG monomer 1 (8.9g), 4-hydroxystyrene (5.4g), PAG monomer 4 (9.7g), and THF (40g) as a solvent were added. The reaction vessel was cooled to -70°C in a nitrogen environment, and the decompression, degassing and nitrogen blowing were repeated 3 times. After the temperature was raised to room temperature, AIBN (1.2g) as a polymerization initiator was added, the temperature was raised to 60°C, and the reaction was allowed to proceed for 15 hours. The reaction solution was added to 1L of isopropanol, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer 8. The composition of polymer 8 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC.

[Synthesis Example 2-9] Synthesis of polymer 9: In a 2L flask, monomer 1 (3.5g), 1-methyl-1-cyclopentyl methacrylate (8.4g), 4-hydroxystyrene (4.2g), PAG monomer 6 (9.4g), and THF (40g) as a solvent were added. The reaction vessel was cooled to -70°C in a nitrogen environment, and the decompression, degassing and nitrogen blowing were repeated 3 times. After the temperature was raised to room temperature, AIBN (1.2g) as a polymerization initiator was added, the temperature was raised to 60°C, and the reaction was allowed to proceed for 15 hours. The reaction solution was added to 1L of isopropanol, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer 9. The composition of polymer 9 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC.

[Synthesis Example 2-10] Synthesis of polymer 10: In a 2L flask, monomer 9 (3.8g), 1-methyl-1-cyclopentyl methacrylate (8.4g), 4-hydroxystyrene (4.2g), PAG monomer 6 (9.4g), and THF (40g) as a solvent were added. The reaction vessel was cooled to -70°C in a nitrogen environment, and the decompression, degassing and nitrogen blowing were repeated 3 times. After the temperature was raised to room temperature, AIBN (1.2g) as a polymerization initiator was added, the temperature was raised to 60°C, and the reaction was allowed to proceed for 15 hours. The reaction solution was added to 1L of isopropanol, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer 10. The composition of polymer 10 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC.

[Synthesis Example 2-11] Synthesis of polymer 11: In a 2L flask, monomer 1 (3.5g), 1-methyl-1-cyclopentyl methacrylate (8.4g), 4-hydroxystyrene (4.2g), PAG monomer 7 (9.6g), and THF (40g) as a solvent were added. The reaction vessel was cooled to -70°C in a nitrogen environment, and the decompression, degassing and nitrogen blowing were repeated 3 times. After the temperature was raised to room temperature, AIBN (1.2g) as a polymerization initiator was added, the temperature was raised to 60°C, and the reaction was allowed to proceed for 15 hours. The reaction solution was added to 1L of isopropanol, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer 11. The composition of polymer 11 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC.

[Synthesis Example 2-12] Synthesis of polymer 12: In a 2L flask, monomer 9 (3.8g), 1-methyl-1-cyclopentyl methacrylate (8.4g), 4-hydroxystyrene (4.2g), PAG monomer 7 (9.6g), and THF (40g) as a solvent were added. The reaction vessel was cooled to -70°C in a nitrogen environment, and the decompression, degassing and nitrogen blowing were repeated 3 times. After the temperature was raised to room temperature, AIBN (1.2g) as a polymerization initiator was added, the temperature was raised to 60°C, and it was reacted for 15 hours. The reaction solution was added to 1L of isopropanol, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer 12. The composition of polymer 12 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC.

[Synthesis Example 2-13] Synthesis of polymer 13: In a 2L flask, monomer 10 (3.8g), 1-vinyl-1-cyclopentyl methacrylate (9.0g), 3-hydroxystyrene (4.2g), PAG monomer 6 (9.4g), and THF (40g) as a solvent were added. The reaction vessel was cooled to -70°C in a nitrogen environment, and the decompression, degassing and nitrogen blowing were repeated 3 times. After the temperature was raised to room temperature, AIBN (1.2g) as a polymerization initiator was added, the temperature was raised to 60°C, and the reaction was allowed to proceed for 15 hours. The reaction solution was added to 1L of isopropanol, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer 13. The composition of polymer 13 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC.

[Synthesis Example 2-14] Synthesis of polymer 14: In a 2L flask, monomer 11 (4.5g), 1-ethynyl-1-cyclopentyl methacrylate (8.9g), 3-hydroxystyrene (4.2g), PAG monomer 8 (9.8g), and THF (40g) as a solvent were added. The reaction vessel was cooled to -70°C in a nitrogen environment, and the decompression, degassing and nitrogen blowing were repeated 3 times. After the temperature was raised to room temperature, AIBN (1.2g) as a polymerization initiator was added, the temperature was raised to 60°C, and the reaction was allowed to proceed for 15 hours. The reaction solution was added to 1L of isopropanol, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer 14. The composition of polymer 14 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC.

[Synthesis Example 2-15] Synthesis of polymer 15: In a 2L flask, monomer 12 (4.6g), 1-ethynyl-1-cyclopentyl methacrylate (8.9g), 3-hydroxystyrene (4.2g), PAG monomer 8 (9.8g), and THF (40g) as a solvent were added. The reaction container was cooled to -70°C in a nitrogen environment, and the decompression, degassing and nitrogen blowing were repeated 3 times. After the temperature was raised to room temperature, AIBN (1.2g) as a polymerization initiator was added, the temperature was raised to 60°C, and it was reacted for 15 hours. The reaction solution was added to 1L of isopropanol, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer 15. The composition of polymer 15 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC.

[Synthesis Example 2-16] Synthesis of polymer 16: Monomer 13 (4.2 g), ALG monomer 1 (8.9 g), 3-hydroxystyrene (4.2 g), PAG monomer 6 (9.4 g), and THF (40 g) as a solvent were added to a 2 L flask. The reaction vessel was cooled to -70°C in a nitrogen environment, and the decompression, degassing and nitrogen blowing were repeated 3 times. After the temperature was raised to room temperature, AIBN (1.2 g) as a polymerization initiator was added, the temperature was raised to 60°C, and the reaction was allowed to proceed for 15 hours. The reaction solution was added to 1 L of isopropanol, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer 16. The composition of polymer 16 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC.

[Synthesis Example 2-17] Synthesis of polymer 17: In a 2L flask, monomer 14 (4.2g), ALG monomer 1 (8.9g), 3-hydroxystyrene (4.2g), PAG monomer 6 (9.4g), and THF (40g) as a solvent were added. The reaction vessel was cooled to -70°C in a nitrogen environment, and the decompression, degassing and nitrogen blowing were repeated 3 times. After the temperature was raised to room temperature, AIBN (1.2g) as a polymerization initiator was added, the temperature was raised to 60°C, and the reaction was allowed to proceed for 15 hours. The reaction solution was added to 1L of isopropanol, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer 17. The composition of polymer 17 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC.

[Synthesis Example 2-18] Synthesis of polymer 18: In a 2L flask, monomer 15 (4.7g), ALG monomer 1 (8.9g), 3-hydroxystyrene (4.2g), PAG monomer 6 (9.4g), and THF (40g) as a solvent were added. The reaction vessel was cooled to -70°C in a nitrogen environment, and the decompression, degassing and nitrogen blowing were repeated 3 times. After the temperature was raised to room temperature, AIBN (1.2g) as a polymerization initiator was added, the temperature was raised to 60°C, and it was reacted for 15 hours. The reaction solution was added to 1L of isopropanol, and the precipitated white solid was filtered. The obtained white solid was dried under reduced pressure at 60°C to obtain polymer 18. The composition of polymer 18 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC.

[Comparative Synthesis Example 1] Synthesis of Comparative Polymer 1 Comparative polymer 1 was obtained in the same manner as in Synthesis Example 2-1 except that monomer 1 was replaced with comparative monomer 1. The composition of comparative polymer 1 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC. [Chemical 157]

[Comparative Synthesis Example 2] Synthesis of Comparative Polymer 2 Comparative polymer 2 was obtained in the same manner as in Synthesis Example 2-1 except that monomer 1 was replaced with comparative monomer 2. The composition of comparative polymer 2 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC. [Chemical 158]

[Comparative Synthesis Example 3] Comparative polymer 3 was obtained by the same method as Synthesis Example 2-1 except that monomer 1 was not used in the synthesis of comparative polymer 3. The composition of comparative polymer 3 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC. [Chem. 159]

[Comparative Synthesis Example 4] Comparative polymer 4 was obtained by the same method as Synthesis Example 2-4 except that monomer 4 was not used in the synthesis of comparative polymer 4. The composition of comparative polymer 4 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC. [Chemical 160]

[Comparative Synthesis Example 5] Synthesis of Comparative Polymer 5 Comparative polymer 5 was obtained in the same manner as in Synthesis Example 2-1 except that monomer 1 was replaced with comparative monomer 3. The composition of comparative polymer 5 was confirmed by ¹³ C-NMR and ¹ H-NMR, and Mw and Mw/Mn were confirmed by GPC. [Chem. 161]

[Examples 1 to 22, Comparative Examples 1 to 5] A solution prepared by dissolving each component in the composition shown in Tables 1 and 2 in an organic solvent in which 50 ppm of the surfactant Polyfox 636 manufactured by OMNOVA was dissolved was filtered with a 0.2 μm filter to obtain a barrier composition.

In Tables 1 and 2, the components are as follows. ･Organic solvent: PGMEA (propylene glycol monomethyl ether acetate) DAA (diacetone alcohol) EL (ethyl lactate) ･Acid generator: PAG-1 (refer to the following structural formula) ･Quencher: Q-1, Q-2, comparative quencher RQ-1 (refer to the following structural formula) [Chemical 162]

[Evaluation of EUV exposure] The resist compositions shown in Tables 1 and 2 were spin-coated on a Si substrate with a 20nm thick spin-coated hard mask SHB-A940 (silicon content of 43 mass%), and pre-baked at 105°C for 60 seconds using a hot plate to obtain a resist film with a thickness of 50nm. It was exposed using an EUV scanning exposure machine NXE3400 manufactured by ASML (NA0.33, σ0.9/0.6, quadrupole illumination, a mask with a hole pattern with a pitch of 46nm on the wafer, +20% bias), and PEB was performed for 60 seconds on a hot plate at the temperature listed in Tables 1 and 2, and developed for 30 seconds using a 2.38 mass% TMAH aqueous solution, to obtain a hole pattern with a size of 23nm. The hole size was measured at the exposure amount when 23nm was formed, and it was taken as the sensitivity. In addition, the size of 50 holes was measured using a length measurement SEM (CG6300) manufactured by Hitachi, Ltd., and the CDU (dimensional variation 3σ) was calculated. The results are shown in Tables 1 and 2.

[Table 1] Polymer (mass) Acid generator (mass fraction) Quenching agent (mass fraction) Organic solvent (mass) PEB temperature (℃) Sensitivity (mJ/cm ² ) CDU (nm) Embodiment 1 Polymer 1 (100) PAG-1 (25.0) - PGMEA(2,000) DAA(500) 80 33 2.7 Embodiment 2 Polymer 2 (100) - - PGMEA(2,000) DAA(500) 80 32 2.4 Embodiment 3 Polymer 3 (100) - - PGMEA(2,000) DAA(500) 80 32 2.9 Embodiment 4 Polymer 4 (100) - - PGMEA(2,000) DAA(500) 80 31 2.4 Embodiment 5 Polymer 5 (100) - - PGMEA(2,000) DAA(500) 80 29 2.5 Embodiment 6 Polymer 6 (100) - - PGMEA(2,000) DAA(500) 80 32 2.4 Embodiment 7 Polymer 7 (100) PAG-1 (10.0) - EL(2,000) PGMEA(500) 80 27 2.6 Embodiment 8 Polymer 7 (100) PAG-1 (15.0) Q-1(3.25) EL(2,000) PGMEA(500) 80 29 2.5 Embodiment 9 Polymer 7 (100) PAG-1 (15.0) Q-2(2.78) EL(2,000) PGMEA(500) 80 29 2.6 Embodiment 10 Polymer 8 (100) - - PGMEA(2,000) DAA(500) 80 32 2.4 Embodiment 11 Polymer 9 (100) - - PGMEA(2,000) DAA(500) 80 30 2.5 Embodiment 12 Polymer 4 (100) - Q-1(0.25) PGMEA(2,000) DAA(500) 80 34 2.1 Embodiment 13 Polymer 5 (100) - Q-1(0.25) PGMEA(2,000) DAA(500) 80 33 2.2 Embodiment 14 Polymer 10 (100) - - PGMEA(2,000) DAA(500) 80 32 2.4 Embodiment 15 Polymer 11 (100) - - PGMEA(2,000) DAA(500) 80 33 2.6 Embodiment 16 Polymer 12 (100) - - PGMEA(2,000) DAA(500) 80 30 2.5 Embodiment 17 Polymer 13 (100) - - PGMEA(2,000) DAA(500) 80 33 2.5 Embodiment 18 Polymer 14 (100) - - PGMEA(1,000) DAA(500) EL(1,000) 80 34 2.4 Embodiment 19 Polymer 15 (100) - - PGMEA(2,000) DAA(500) 80 33 2.6 Embodiment 20 Polymer 16 (100) - - PGMEA(2,000) DAA(500) 80 30 2.5 Embodiment 21 Polymer 17 (100) - - PGMEA(2,000) DAA(500) 80 31 2.4 Embodiment 22 Polymer 18 (100) - - PGMEA(2,000) DAA(500) 80 30 2.4

[Table 2] Polymer (mass) Acid generator (mass fraction) Quenching agent (mass fraction) Organic solvent (mass) PEB temperature (℃) Sensitivity (mJ/cm ² ) CDU (nm) Comparative example 1 Compare polymer 1 (100) PAG-1 (25.0) - PGMEA(2,000) DAA(500) 80 45 4.1 Comparative example 2 Compare polymers 2 (100) PAG-1 (25.0) - PGMEA(2,000) DAA(500) 80 48 4.3 Comparative example 3 Compare polymers 3 (100) PAG-1 (25.0) RQ-1 (4.00) PGMEA(2,000) DAA(500) 80 41 4.0 Comparative example 4 Compare polymers 4 (100) - RQ-1 (4.00) PGMEA(2,000) DAA(500) 80 34 3.3 Comparative example 5 Compare Polymer 5 (100) PAG-1 (25) - PGMEA(2,000) DAA(500) 80 46 3.8

As shown in Tables 1 and 2, the resist composition containing the resist material of the present invention using a specific polymer, wherein the specific polymer contains a repeating unit a having a structure of a stibnium salt or an iodonium salt of a monovalent aromatic carboxylic acid substituted with iodine, satisfies sufficient sensitivity and dimensional uniformity (Examples 1 to 22). In contrast, Comparative Examples 1 to 5 using the resist composition not containing the resist material of the present invention result in poor sensitivity and dimensional uniformity.

This specification includes the following aspects. [1]: A resist material, characterized in that it contains a repeating unit a, wherein the repeating unit a contains a substituted or unsubstituted iodinated monovalent aromatic carboxylic acid codon or iodonium salt bonded to the polymer main chain via an ester bond. [2]: The resist material as described in [1] above, characterized in that the repeating unit a contains a repeating unit represented by the following general formula (a)-1 or (a)-2. [Chemistry 163] In the formula, ^RA is a hydrogen atom or a methyl group. ^X1' is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing an ester bond or an ether bond, and may also have one or more selected from a halogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a nitro group, and a cyano group. ^X2 is a single bond or a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and may also contain one or more selected from an ester group, an ether group, an amide group, a lactone ring, a sultone ring, and a halogen atom. ^X3 is a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms and not containing a fluorine atom, and may also have one or more selected from an ether group and an ester group. Y is a group selected from an ester group and a sulfonate group. ^R1 is independently a linear or branched alkyl group, alkoxy group, acyloxy group, or halogen atom other than iodine having 1 to 4 carbon atoms. m is an integer of 1 to 4, and n is an integer of 0 to 3. ^R2 to ^R6 are independently a monovalent alkyl group having 1 to 25 carbon atoms which may contain a heteroatom. In addition, any two of ^R2 , ^R3 , and ^R4 may be bonded to each other and form a ring together with the sulfur atom to which they are bonded. [3]: The resist material of [2], characterized in that: in the general formulas (a)-1 and (a)-2, the ^X2 is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and may contain at least one selected from an ester group, an ether group, an amide group, a lactone ring, a sultone ring, and a halogen atom. [4]: The resist material of any one of [1] to [3], characterized in that: it further contains a repeating unit b in which the hydrogen atoms of either or both of a carboxyl group and a phenolic hydroxyl group are substituted with an acid-labile group. [5]: The resist material of [4], characterized in that: the repeating unit b is at least one selected from the repeating units represented by the following general formulas (b1) and (b2). [Chemistry 164] In the formula, ^RA is independently a hydrogen atom or a methyl group. ^Y1 is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and having an ester bond, an ether bond, or a lactone ring. ^Y2 is a single bond, an ester bond, or an amide bond. ^R11 and ^R12 are acid-unstable groups. ^R13 is a fluorine atom, a trifluoromethyl group, a cyano group, or an alkyl group having 1 to 6 carbon atoms. ^R14 is a single bond or a linear or branched alkanediyl group having 1 to 6 carbon atoms, and a portion of the carbon atoms thereof may be substituted by an ether bond or an ester bond. a is 1 or 2. b is an integer of 0 to 4. [6]: The resist material as described in any one of [1] to [5] above, characterized in that the resist material further contains a repeating unit c having an adhesive group selected from a hydroxyl group, a carboxyl group, a lactone ring, a carbonate group, a thiocarbonate group, a carbonyl group, a cyclic acetal group, an ether bond, an ester bond, a sulfonate bond, a cyano group, an amide group, -OC(=O)-S-, and -OC(=O)-NH-. [7]: The resist material as described in any one of [1] to [6] above, characterized in that the resist material further contains a repeating unit d of at least one type selected from the repeating units represented by the following general formulas (d1) to (d3). [Chemistry 165] In the formula, ^RA is independently a hydrogen atom or a methyl group. ^Z1 is a single bond, a phenylene group, ^-OZ11- , -C(=O) ^-OZ11- or -C(=O)-NH- ^Z11- , ^Z11 is an alkanediyl group having 1 to 6 carbon atoms, an alkenediyl group having 2 to 6 carbon atoms or a phenylene group, and may contain at least one selected from a carbonyl group, an ester bond, an ether bond, and a hydroxyl group. ^{Z2A is a single bond or an ester bond. Z2B} is a single ^bond or a divalent group having 1 to 12 carbon atoms, and may contain at least one selected from an ester bond, an ether bond, a lactone ring, a bromine atom, and an iodine atom. Z ³ is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, -OZ ³¹ -, -C(=O)-OZ ³¹ - or -C(=O)-NH-Z ³¹ -, Z ³¹ is an alkanediyl group having 1 to 6 carbon atoms, an alkenediyl group having 2 to 6 carbon atoms or a phenylene group, and may contain at least one selected from a carbonyl group, an ester bond, an ether bond, a halogen atom, and a hydroxyl group. Rf ¹ to Rf ⁴ are independently a hydrogen atom, a fluorine atom or a trifluoromethyl group, but at least one of them is a fluorine atom. R ²¹ to R ²⁸ are independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may contain a heteroatom. Furthermore, any two of R ²³ , R ²⁴ and R ²⁵ or any two of R ²⁶ , R ²⁷ and R ²⁸ may be bonded to each other and form a ring together with the sulfur atom to which they are bonded. ^{M- is} a non-nucleophilic relative ion. [8]: The resist material as described in [7] above, characterized in that the Z ^2B contains at least one iodine atom. [9]: The resist material as described in any one of [1] to [8] above, characterized in that the molecular weight of the resist material is in the range of 1,000 to 100,000. [10]: A resist composition, characterized in that it contains the resist material as described in any one of [1] to [9] above. [11]: The resist composition of the above-mentioned [10] is characterized in that it further contains one or more selected from an acid generator, an organic solvent, a quencher, and a surfactant. [12]: A pattern forming method comprises the following steps: forming a resist film on a substrate using the resist composition of the above-mentioned [10] or [11], exposing the resist film to high-energy radiation, and developing the exposed resist film using a developer. [13]: The pattern forming method of the above-mentioned [12] is characterized in that i-rays, KrF excimer laser light, ArF excimer laser light, electron beams, or extreme ultraviolet rays with a wavelength of 3 to 15 nm are used as the high-energy radiation. [14]: A monomer characterized by being represented by the following general formula (a)-1M or (a)-2M. [Chemistry 166] In the formula, ^RA is a hydrogen atom or a methyl group. ^X1 is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing an ester bond or an ether bond, and may also have a halogen atom. ^X2 is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and may also contain one or more selected from an ester group, an ether group, an amide group, a lactone ring, a sultone ring, and a halogen atom. ^X3 is a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms and not containing a fluorine atom, and may also have one or more selected from an ether group and an ester group. ^R1 is independently a linear or branched alkylene group having 1 to 4 carbon atoms, an alkoxy group, an acyloxy group, or a halogen atom other than iodine. m is an integer of 1 to 4, and n is an integer of 0 to 3. R ² to R ⁶ are independently a monovalent hydrocarbon group having 1 to 25 carbon atoms which may contain a heteroatom. In addition, any two of R ² , R ³ and R ⁴ may be bonded to each other and form a ring together with the sulfur atom to which they are bonded. [15]: A monomer characterized by being represented by the following general formula (a)-1'M or (a)-2'M. [Chem. 167] In the formula, ^RA is a hydrogen atom or a methyl group. ^X1' is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing an ester bond or an ether bond, and may also have one or more selected from a halogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a nitro group, and a cyano group. ^X2 is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and may also contain one or more selected from an ester group, an ether group, an amide group, a lactone ring, a sultone ring, and a halogen atom. ^X3 is a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms and not containing a fluorine atom, and may also have one or more selected from an ether group and an ester group. Y is a group selected from an ester group and a sulfonate group. ^R1 is independently a linear or branched alkyl group, alkoxy group, acyloxy group, or halogen atom other than iodine having 1 to 4 carbon atoms. m is an integer of 1 to 4, and n is an integer of 0 to 3. ^R2 to ^R6 are independently a monovalent alkyl group having 1 to 25 carbon atoms which may contain a heteroatom. In addition, any two of ^R2 , ^R3 , and ^R4 may be bonded to each other and form a ring together with the sulfur atom to which they are bonded.

In addition, the present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are for illustration only, and those having substantially the same structure and exerting the same effects as the technical concept described in the scope of the patent application of the present invention are all included in the technical scope of the present invention.

without

[Figure 1] is a diagram showing ^{the 1} H-NMR (500 MHz, DMSO-d ₆ ) spectrum of compound 2 synthesized in Synthesis Example 1-1. [Figure 2] is a diagram showing ^{the 1} H-NMR (500 MHz, DMSO-d ₆ ) spectrum of compound 3 synthesized in Synthesis Example 1-1. [Figure 3] is a diagram showing ^{the 1} H-NMR (500 MHz, DMSO-d ₆ ) spectrum of compound 4 synthesized in Synthesis Example 1-1. [Figure 4] is a diagram showing the ¹ H-NMR (500 MHz, DMSO-d ₆ ) spectrum of monomer 1 synthesized in Synthesis Example 1-1.

Claims (13)

A resist material characterized by comprising a repeating unit a, wherein the repeating unit a comprises a substituted or unsubstituted iodinated monovalent aromatic carboxylic acid coronium salt or iodonium salt bonded to a polymer main chain via an ester bond, wherein the repeating unit a comprises a repeating unit represented by the following general formula (a)-1 or (a)-2; In the formula, ^RA is a hydrogen atom or a methyl group; X1 ^' is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing an ester bond or an ether bond, and may also have one or more selected from a halogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a nitro group, and a cyano group; ^X2 is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and may also contain one or more selected from an ester group, an ether group, an amide group, a sultone ring, and a halogen atom; ^X3 is a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms and not containing a fluorine atom, and may also have one or more selected from an ether group and an ester group; Y is a group selected from an ester group and a sulfonate group; R ¹ is independently a linear or branched alkyl group, alkoxy group, acyloxy group, or halogen atom other than iodine having 1 to 4 carbon atoms; m is an integer of 1 to 4, and n is an integer of 0 to 3; R ² to R ⁶ are independently a monovalent hydrocarbon group having 1 to 25 carbon atoms which may contain a heteroatom; and any two of R ² , R ³ and R ⁴ may be bonded to each other and form a ring together with the sulfur atom to which they are bonded. The inhibitor material of claim 1 further comprises repeating units b in which the hydrogen atoms of either or both of the carboxyl group and the phenolic hydroxyl group are replaced by acid-labile groups. The resist material of claim 2, wherein the repeating unit b is at least one selected from the repeating units represented by the following general formulae (b1) and (b2); In the formula, ^RA is independently a hydrogen atom or a methyl group; ^Y1 is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and having an ester bond or an ether bond; ^Y2 is a single bond, an ester bond, or an amide bond; ^R11 and ^R12 are acid-labile groups; ^R13 is a fluorine atom, a trifluoromethyl group, a cyano group, or an alkyl group having 1 to 6 carbon atoms; ^R14 is a single bond or a linear or branched alkanediyl group having 1 to 6 carbon atoms, and a portion of the carbon atoms thereof may be substituted by an ether bond or an ester bond; a is 1 or 2; and b is an integer of 0 to 4. The resist material of claim 1, wherein the resist material further contains repeating units c having an adhesion group selected from hydroxyl, carboxyl, carbonate, thiocarbonate, carbonyl, cyclic acetal, ether, ester, sulfonate, cyano, amide, -O-C(=O)-S-, and -O-C(=O)-NH-. The resist material of claim 1, wherein the resist material further comprises at least one repeating unit d selected from the repeating units represented by the following general formulas (d1) to (d3); wherein ^RA is independently a hydrogen atom or a methyl group; ^Z1 is a single bond, a phenylene group, ^-OZ11- , -C(=O) ^-OZ11- , or -C(=O)-NH- ^Z11- ; ^Z11 is an alkanediyl group having 1 to 6 carbon atoms, an alkenediyl group having 2 to 6 carbon atoms, or a phenylene group, and may contain at least one selected from a carbonyl group, an ester bond, an ether bond, and a hydroxyl group; ^Z2A is a single bond or an ester bond; ^Z2B is a single bond or a divalent group having 1 to 12 carbon atoms, and may contain at least one selected from an ester bond, an ether bond, a bromine atom, and an iodine atom; ^Z3 is a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, ^-OZ31- , -C(=O) ^-OZ31- , or -C(=O)-NH- ^Z31 -, Z ³¹ is an alkanediyl group having 1 to 6 carbon atoms, an alkenediyl group having 2 to 6 carbon atoms, or a phenylene group, and may contain one or more selected from a carbonyl group, an ester bond, an ether bond, a halogen atom, and a hydroxyl group; Rf ¹ to Rf ⁴ are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one of them is a fluorine atom; R ²¹ to R ²⁸ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, which may contain a heteroatom; and any two of R ²³ , R ²⁴ , and R ²⁵ or any two of R ²⁶ , R ²⁷ , and R ²⁸ may be bonded to each other and form a ring together with the sulfur atom to which they are bonded; M ^- is a non-nucleophilic relative ion. The resist material of claim 5, wherein Z ^2B contains at least one iodine atom. The resist material of claim 1, wherein the weight average molecular weight of the resist material is in the range of 1,000 to 100,000. A resist composition, characterized by containing the resist material as described in any one of claims 1 to 7. The inhibitor composition of claim 8 further contains at least one selected from an acid generator, an organic solvent, a quencher, and a surfactant. A pattern forming method comprises the following steps: Using the resist composition as claimed in claim 8 to form a resist film on a substrate, Exposing the resist film to high-energy radiation, and Developing the exposed resist film using a developer. The pattern forming method of claim 10 uses i-rays, KrF excimer laser light, ArF excimer laser light, electron beams, or extreme ultraviolet light with a wavelength of 3 to 15 nm as the high-energy radiation. A monomer characterized by being represented by the following general formula (a)-1M or (a)-2M; In the formula, ^RA is a hydrogen atom or a methyl group; ^X1 is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing an ester bond or an ether bond, and may also have a halogen atom; ^X2 is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and may also contain one or more selected from an ester group, an ether group, an amide group, a sultone ring, and a halogen atom; ^X3 is a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms and not containing a fluorine atom, and may also have one or more selected from an ether group and an ester group; ^R1 is independently a linear or branched alkylene group having 1 to 4 carbon atoms, an alkoxy group, an acyloxy group, or a halogen atom other than iodine; m is an integer of 1 to 4, and n is an integer of 0 to 3; ^R2 to R ^{6 are} each independently a monovalent hydrocarbon group having 1 to 25 carbon atoms which may contain a heteroatom; and any two of R ² , R ³ and R ⁴ may be bonded to each other and form a ring together with the sulfur atom to which they are bonded. A monomer characterized by being represented by the following general formula (a)-1'M or (a)-2'M; In the formula, ^RA is a hydrogen atom or a methyl group; X1 ^' is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing an ester bond or an ether bond, and may also have one or more selected from a halogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a nitro group, and a cyano group; ^X2 is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and may also contain one or more selected from an ester group, an ether group, an amide group, a sultone ring, and a halogen atom; ^X3 is a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms and not containing a fluorine atom, and may also have one or more selected from an ether group and an ester group; Y is a group selected from an ester group and a sulfonate group; R ¹ is independently a linear or branched alkyl group, alkoxy group, acyloxy group, or halogen atom other than iodine having 1 to 4 carbon atoms; m is an integer of 1 to 4, and n is an integer of 0 to 3; R ² to R ⁶ are independently a monovalent hydrocarbon group having 1 to 25 carbon atoms which may contain a heteroatom; and any two of R ² , R ³ and R ⁴ may be bonded to each other and form a ring together with the sulfur atom to which they are bonded.

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